U.S. patent number 7,566,362 [Application Number 12/173,422] was granted by the patent office on 2009-07-28 for ink, ink jet recording method, ink cartridge, recording unit and ink jet recording apparatus.
This patent grant is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Kuniaki Fujimoto, Yojiro Kojima, Otome Mori, Daiji Okamura, Jun Yoshizawa.
United States Patent |
7,566,362 |
Mori , et al. |
July 28, 2009 |
Ink, ink jet recording method, ink cartridge, recording unit and
ink jet recording apparatus
Abstract
An ink containing at least two coloring materials of a first
coloring material and a second coloring material, wherein the first
coloring material is a compound represented by the general formula
(I), and the second coloring material is a compound represented by
the general formula (II): ##STR00001##
Inventors: |
Mori; Otome (Yokohama,
JP), Fujimoto; Kuniaki (Chofu, JP), Kojima;
Yojiro (Tokyo, JP), Yoshizawa; Jun (Tokyo,
JP), Okamura; Daiji (Yokohama, JP) |
Assignee: |
Canon Kabushiki Kaisha (Tokyo,
JP)
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Family
ID: |
39873943 |
Appl.
No.: |
12/173,422 |
Filed: |
July 15, 2008 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20090047430 A1 |
Feb 19, 2009 |
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Foreign Application Priority Data
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Aug 10, 2007 [JP] |
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2007-210095 |
Jul 4, 2008 [JP] |
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2008-175247 |
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Current U.S.
Class: |
106/31.48;
106/31.47; 347/100 |
Current CPC
Class: |
C09D
11/32 (20130101); C09D 11/328 (20130101); C09B
67/0041 (20130101); C09B 67/0046 (20130101) |
Current International
Class: |
C09D
11/02 (20060101); B41J 2/01 (20060101) |
Field of
Search: |
;106/31.48,31.47
;347/100 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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0 418 792 |
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Mar 1991 |
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EP |
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1 767 595 |
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Mar 2007 |
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EP |
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57-44605 |
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Mar 1982 |
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JP |
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8-73791 |
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Mar 1996 |
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JP |
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2803134 |
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Jul 1998 |
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JP |
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2881847 |
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Feb 1999 |
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JP |
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2002-80765 |
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Mar 2002 |
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JP |
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2002-249677 |
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Sep 2002 |
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JP |
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2002-275386 |
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Sep 2002 |
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JP |
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2002-294097 |
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Oct 2002 |
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JP |
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2002-302623 |
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Oct 2002 |
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JP |
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2002-327132 |
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Nov 2002 |
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JP |
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2003-3099 |
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Jan 2003 |
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JP |
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2003-34758 |
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Feb 2003 |
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JP |
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2003-213168 |
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Jul 2003 |
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JP |
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2005-139427 |
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Jun 2005 |
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JP |
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2006-45535 |
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Feb 2006 |
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JP |
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2006-143989 |
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Jun 2006 |
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JP |
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3851569 |
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Sep 2006 |
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JP |
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2006-526062 |
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Nov 2006 |
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JP |
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WO 2004/099328 |
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Nov 2004 |
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WO |
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WO 2004/104108 |
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Dec 2004 |
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WO |
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WO 2006/001274 |
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Jan 2006 |
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WO |
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Other References
Nov. 7, 2008 European Search Report in European Patent Appln. No.
08160972.9. cited by other.
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Primary Examiner: Klemanski; Helene
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper &
Scinto
Claims
What is claimed is:
1. An ink comprising at least two coloring materials of a first
coloring material and a second coloring material, wherein the first
coloring material is a compound represented by the following
general formula (I), and the second coloring material is a compound
represented by the following general formula (II): ##STR00074##
wherein A, B, C and D are, independently of one another, an
aromatic six-membered ring, M is a hydrogen atom, alkali metal,
ammonium or organic ammonium, E is an alkylene group, X is a
sulfo-substituted anilino group, carboxyl-substituted anilino group
or phosphono-substituted anilino group, with the proviso that such
a substituted anilino group may further have 1 to 4 substituents
selected from the group consisting of sulfonic, carboxyl,
phosphono, sulfamoyl, carbamoyl, hydroxyl, alkoxy, amino,
alkylamino, dialkylamino, arylamino, diarylamino, acetylamino,
ureido, alkyl, nitro, cyano, alkylsulfonyl and alkylthio groups and
halogen atoms, Y is a hydroxyl group or amino group, and l, m and n
have the following relationship: 0.ltoreq.l.ltoreq.2,
0.ltoreq.m.ltoreq.3, 0.1.ltoreq.n.ltoreq.3 and l+m+n=1 to 4; and
##STR00075## wherein R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2 are,
independently of one another, a monovalent group, X.sub.1 and
X.sub.2 are, independently of each other, an electron attractive
group having a Hammett's .sigma.p value of 0.20 or more, Z.sub.1
and Z.sub.2 are, independently of each other, a hydrogen atom,
substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl
group, substituted or unsubstituted aralkyl group, substituted or
unsubstituted aryl group, or substituted or unsubstituted
heterocyclic group, and M is a hydrogen atom, alkali metal,
ammonium or organic ammonium.
2. The ink according to claim 1, wherein at least one of A, B, C
and D in the general formula (I) is a pyridine ring or a pyrazine
ring.
3. The ink according to claim 1, wherein the content (% by mass) of
the first coloring material in the ink is from 0.1 times or more to
15.0 times or less in terms of mass ratio to the content (% by
mass) of the second coloring material in the ink.
4. The ink according to claim 1, which further comprises, as a
third coloring material, at least one compound selected from the
group consisting of a compound represented by the following general
formula (III), a compound represented by the following general
formula (IV) and a compound represented by the following general
formula (V): ##STR00076## wherein R are, independently of each
other, a hydrogen atom, alkyl group, hydroxyalkyl group, cyclohexyl
group monoalkylaminoalkyl group or dialkylaminoalkyl group, M's
are, independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium, and X is a linking group;
##STR00077## wherein R.sub.1 is a hydrogen atom or alkyl group, m
is an integer of 1 to 3, and M's are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium; and
##STR00078## wherein R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are,
independently of one another, an alkyl group, and M's are,
independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium.
5. The ink according to claim 1, wherein the content (% by mass) of
the third coloring material in the ink is from 0.5 times or more to
5.0 times or less in terms of mass ratio to the total of the
content (% by mass) of the first coloring material and the content
(% by mass) of the second coloring material in the ink.
6. The ink according to claim 4, wherein the third coloring
material is the compound represented by the general formula
(V).
7. The ink according to claim 1, which further comprises, as a
fourth coloring material, at least one compound selected from the
group consisting of a compound represented by the following general
formula (VI) and a compound represented by the following general
formula (VII): ##STR00079## wherein R.sub.10 are, independently of
each other, a hydrogen atom, hydroxyl group, carboxyl group, an
alkyl group having 1 to 4 carbon atoms, which may be substituted by
a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, an
alkoxy group having 1 to 4 carbon atoms, which may be substituted
by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms,
an alkylamino group having 1 to 4 carbon atoms, which may be
substituted by a hydroxyl group or an alkoxy group having 1 to 4
carbon atoms, a carboxy-(C1-C5)alkylamino group, a
bis[carboxy-(C1-C5)alkyl]amino group, an alkanoylamino group having
1 to 4 carbon atoms, which may be substituted by a hydroxyl group
or an alkoxy group having 1 to 4 carbon atoms, a phenylamino group,
which may be substituted by a carboxyl, sulfonic or amino group, a
sulfonic group, a halogen atom, or a ureido group, [C] is an
aliphatic amine residue having a carboxyl or sulfonic group, and
M's are, independently of one another, a hydrogen atom, alkali
metal, ammonium or organic ammonium; and ##STR00080## wherein A is
an aromatic or heterocyclic group which may be substituted, B is
any one of groups represented by the following general formulae (1)
to (5), and M's are, independently of each other, a hydrogen atom,
alkali metal, ammonium or organic ammonium, ##STR00081## wherein
R.sub.1 to R.sub.9 are, independently of one another, a hydrogen
atom, halogen atom, aliphatic group, aromatic group, heterocyclic
group, carboxyl group, carbamoyl group, alkoxycarbonyl group,
aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group,
hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy
group, silyloxy group, acyloxy group, carbamoyloxy group,
alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group,
acylamino group, ureido group, sulfamoylamino group,
alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl- or
arylsulfonylamino group, heterocyclic sulfonylamino group, cyano
group, nitro group, alkyl- or arylthio group, heterocyclic thio
group, alkyl- or arylsulfonyl group, heterocyclic sulfonyl group,
alkyl- or arylsulfinyl group, heterocyclic sulfinyl group,
sulfamoyl group, or sulfonic group, with the proviso that each
group may be further substituted.
8. The ink according to claim 7, wherein the content (% by mass) of
the fourth coloring material in the ink is from 1.0 time or more to
70.0 times or less in terms of mass ratio to the total of the
content (% by mass) of the first coloring material, the content (%
by mass) of the second coloring material and the content (% by
mass) of the third coloring material in the ink.
9. The ink according to claim 7, wherein the fourth coloring
material is the compound represented by the general formula
(VII).
10. An ink jet recording method comprising ejecting an ink by an
ink jet system to conduct recording on a recording medium, wherein
the ink is the ink according to claim 1.
11. An ink cartridge comprising an ink storage portion for storing
an ink, wherein the ink is the ink according to claim 1.
12. A recording unit comprising an ink storage portion for storing
an ink and a recording head for ejecting the ink, wherein the ink
is the ink according to claim 1.
13. An ink jet recording apparatus comprising an ink storage
portion for storing an ink and a recording head for ejecting the
ink, wherein the ink is the ink according to claim 1.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an ink, an ink jet recording
method, an ink cartridge, a recording unit and an ink jet recording
apparatus.
2. Description of the Related Art
An ink jet recording method is a recording method that minute
droplets of an ink are applied to a recording medium such as plain
paper or glossy medium, thereby forming an image, and is rapidly
spread because of lowered price of an apparatus itself and
improvement of recording speed. With the rapid spread of digital
cameras in addition to the progress of the formation of
high-quality images by the ink jet recording method, the ink jet
recording method becomes general as an output method of images
comparable with a silver halide photograph.
In recent years, there has been a demand for outputting a recorded
article having image quality comparable with that of a silver
halide photograph, in particular, a recorded article with reduced
feeling of grain, excellent gradation property, which has image
quality better than ever, with the spread of ink jet recording
apparatus.
In order to solve such a problem, it is conducted to use a gray ink
having a neutral color tone in addition to conventional respective
inks of cyan, magenta and yellow. It is known that the use of the
gray ink in addition to the conventional inks improves, for
example, a feeling of grain in a shadow portion such as a flesh
color or background portion, or gradation property upon gradation
from a highlight to a shadow to obtain a recorded article having
higher image quality. Incidentally, the meaning that an ink has a
neutral color tone will be described subsequently.
A gray ink is generally prepared by conducting toning with coloring
materials of cyan, magenta and yellow. It has been proposed to
improve image quality by using the gray ink prepared by using such
coloring material in combination. For example, it has been proposed
to provide a light gray ink, a medium gray ink and a dark gray ink
as toned gray inks to conduct gradation recording by combination of
these inks (see Japanese Unexamined Patent Publication No.
2006-526062). This publication also discloses that a black coloring
material is mixed with a proper coloring material to provide an
gray ink.
On the other hand, the gray ink by the combination of cyan, magenta
and yellow involves a problem that the image-storing ability of the
resulting recorded article is low compared with the silver halide
photograph. Specifically, when the recorded article formed with the
gray ink is exposed to light, humidity or an environmental gas
present in the air for a long period of time, a problem that a
coloring material on the recorded article is deteriorated, and so
change of color tone of the image or color fading is easy to occur
arises. A large number of proposals has heretofore been made for
improving the ozone fastness and light fastness of the image in
particular in this image-storing ability.
The color fading of the image is mainly caused by the cyan ink
particularly low in the ozone fastness among the respective inks of
cyan, yellow and magenta. Therefore, a large number of proposals
has been made for improving the ozone fastness of the cyan ink (see
Japanese Patent Application Laid-Open Nos. 2002-249677,
2002-275386, 2002-294097, 2002-302623, 2002-327132, 2003-003099 and
2003-213168). In addition, a proposal has been made on the
improvement in the ozone fastness of an image by introducing a
nitrogen-containing aromatic heterocyclic ring into the skeleton of
a phthalocyanine coloring material commonly used as a coloring
material of the cyan ink (see Japanese Patent Application Laid-Open
No. 2003-34758). It is described that this phthalocyanine coloring
material may have (SO.sub.3D).sub.m or (SO.sub.2NHR).sub.n (m=1 to
4, n=0 to 3) as a substituent, and SO.sub.2NHR is SO.sub.2NH.sub.2
or a sulfonamide residue capable of forming a complex with a copper
ion. Incidentally, D is a monovalent alkali metal, ammonium or
organic ammonium.
Japanese Patent Application Laid-Open No. 2003-034758 describes
that SO.sub.2NH.sub.2 is favorable as SO.sub.2NHR. However, three
Examples among five Examples in Japanese Patent Application
Laid-Open No. 2003-034758 are examples where the phthalocyanine
coloring material has no SO.sub.2NHR, i.e., n is 0. The results of
a color fading test with ozone gas when phthalocyanine coloring
materials having SO.sub.2NH.sub.2 as SO.sub.2NHR and substituted by
a sulfonamide residue were respectively used are described.
However, it is disclosed that the results of the color fading test
when these phthalocyanine coloring materials were used are poorer
than the case of n=0 though Japanese Patent Application Laid-Open
No. 2003-034758 describes that SO.sub.2NH.sub.2 is favorable as
SO.sub.2NHR as described above.
The performance required of a recorded article obtained by the ink
jet recording method for the ozone fastness is increased year by
year, and so the coloring material heretofore used in the cyan ink
does not come to provide an image having ozone resistance on the
level satisfying the above requirement. For example, in the
inventions described in Japanese Patent Application Laid-Open Nos.
2002-249677, 2002-275386, 2002-294097, 2002-302623, 2002-327132,
2003-003099, 2003-213168 and 2003-034758, it is attempted to
improve the ozone fastness of the image by introducing various
substituents into the coloring material. However, there is a limit
to improve the ozone fastness of the image by only the properties
of such a coloring material.
SUMMARY OF THE INVENTION
As described above, a gray ink having performance required of the
gray ink and being capable of providing an image having ozone
fastness and light fastness on a high level has not been present to
date. It is accordingly a first object of the present invention to
provide a gray ink having performance required of the gray ink and
being capable of providing an image having ozone fastness and light
fastness on a high level.
A recorded article formed with the gray ink making combined use of
the cyan, magenta and yellow coloring materials involves a problem
that a color difference becomes great according to a light source
(reflected light), i.e., metamerism is poor. Incidentally, the
metamerism means a phenomenon that colors different in spectral
distribution look the same color under certain observation
conditions. However, in the present invention, the metamerism means
a phenomenon that the color of a recorded article looks different
according to a light source (reflected light, not transmitted
light). When the metamerism of the recorded article is poor, such a
recorded article involves a problem that the color thereof looks
different under sunlight and fluorescent lamps. Accordingly, it is
a second problem of the present invention to provide a gray ink
capable of solving or reducing the problem of metamerism.
The present inventors have carried out an investigation as to
images obtained with toned gray inks making combined use of various
cyan dyes, magenta dyes and yellow dyes. As a result, the following
fact has been found. A phthalocyanine dye widely used as a cyan dye
applied to ink jet inks on a recording medium is generally liable
to be present in the vicinity of the surface of the recording
medium. Therefore, it has been found that the phthalocyanine dye is
easy to be damaged by oxide gases such as ozone gas in the air and
has a tendency to be more deteriorated compared with dyes of other
color tones. The present inventors have carried out a further
investigation based on such finding and found the following fact.
Specifically, it has been found that when an image obtained with a
gray ink toned by a cyan dye, a magenta dye and a yellow dye is
exposed to ozone gas, a cyan component is markedly deteriorated
compared with other components.
Thus, the present inventors have sought cyan, magenta and yellow
dyes as main elements capable of inhibiting the deterioration of a
cyan component and achieving ozone fastness on a high level when
used in the formation of an image. As a result, it has been found
that a specific cyan dye and a specific yellow dye are used in
combination, whereby the behavior of the cyan dye in a recording
medium is markedly changed compared with conventional cyan dyes. It
has been further found that the combined use of such specific dyes
permits inhibiting the deterioration of a cyan component and
thereby achieving the ozone fastness of the resulting image on a
high level. Accordingly, it is a third object of the present
invention to analyze the behavior of a cyan dye in a recording
medium, thereby providing an ink making combined use of the
specific cyan dye and specific yellow dye and providing an image
capable of achieving the ozone fastness on a high level.
The present inventors have further found that a gray ink providing
an image excellent in ozone fastness and color tone is obtained by
using a specific magenta dye in combination with the specific cyan
dye and yellow dye. It has also been found that a specific dye is
used in combination with the above-described dyes, thereby
obtaining a gray ink, which provides an image excellent in ozone
fastness and light fastness, having a color tone favorable as a
gray ink and also excellent in metamerism.
As apparent from the recognition of the above problems, it is an
object of the present invention to provide respective inventions
solving the above respective problems. Specifically, the object is
to provide an ink providing an image excellent in ozone fastness
and having a neutral gray color tone. Another object of the present
invention is to provide an ink providing an image excellent in
light fastness. A further object of the present invention is to
provide an ink providing an image excellent in metamerism. A still
further object of the present invention is to provide an ink jet
recording method, an ink cartridge, a recording unit and an ink jet
recording apparatus using any one of the above-described inks.
Methods for solving the above respective problems correspond to the
respective objects. More specifically, an ink according to the
present invention is an ink comprising at least two coloring
materials of a first coloring material and a second coloring
material, wherein the first coloring magerial is a compound
represented by the following general formula (I), and the second
coloring material is a compound represented by the following
general formula (II):
##STR00002## wherein A, B, C and D are, independently of one
another, an aromatic six-membered ring, M is a hydrogen atom,
alkali metal, ammonium or organic ammonium, E is an alkylene group,
X is a sulfo-substituted anilino group, carboxyl-substituted
anilino group or phosphono-substituted anilino group, with the
proviso that such a substituted anilino group may further have 1 to
4 substituents selected from the group consisting of sulfonic,
carboxyl, phosphono, sulfamoyl, carbamoyl, hydroxyl, alkoxy, amino,
alkylamino, dialkylamino, arylamino, diarylamino, acetylamino,
ureido, alkyl, nitro, cyano, alkylsulfonyl and alkylthio groups and
halogen atoms, Y is a hydroxyl group or amino group, and l, m and n
have the following relationship: 0.ltoreq.l.ltoreq.2,
0.ltoreq.m.ltoreq.3, 0.1.ltoreq.n.ltoreq.3 and l+m+n=1 to 4;
and
##STR00003## wherein R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2 are,
independently of one another, a monovalent group, X.sub.1 and
X.sub.2 are, independently of each other, an electron attractive
group having a Hammett's .sigma.p value of 0.20 or more, Z.sub.1
and Z.sub.2 are, independently of each other, a hydrogen atom,
substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl
group, substituted or unsubstituted aralkyl group, substituted or
unsubstituted aryl group, or substituted or unsubstituted
heterocyclic group, and M is a hydrogen atom, alkali metal,
ammonium or organic ammonium.
An ink according to another embodiment of the present invention
further comprises, as a third coloring material, at least one
compound selected from the group consisting of a compound
represented by the following general formula (III), a compound
represented by the following general formula (IV) and a compound
represented by the following general formula (V):
##STR00004## wherein R are, independently of each other, a hydrogen
atom, alkyl group, hydroxyalkyl group, cyclohexyl group
monoalkylaminoalkyl group or dialkylaminoalkyl group, M's are,
independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium, and X is a linking group;
##STR00005## wherein R.sub.1 is a hydrogen atom or alkyl group, m
is an integer of 1 to 3, and M's are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium;
and
##STR00006## wherein R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are,
independently of one another, an alkyl group, and M's are,
independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium.
An ink according to a further embodiment of the present invention
further comprises, as a fourth coloring material, at least one
compound selected from the group consisting of a compound
represented by the following general formula (VI) and a compound
represented by the following general formula (VII):
##STR00007## wherein R.sub.10 are, independently of each other, a
hydrogen atom, hydroxyl group, carboxyl group, an alkyl group
having 1 to 4 carbon atoms, which may be substituted by a hydroxyl
group or an alkoxy group having 1 to 4 carbon atoms, an alkoxy
group having 1 to 4 carbon atoms, which may be substituted by a
hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, an
alkylamino group having 1 to 4 carbon atoms, which may be
substituted by a hydroxyl group or an alkoxy group having 1 to 4
carbon atoms, a carboxy-(C1-C5)alkylamino group, a
bis[carboxy-(C1-C5)alkyl]amino group, an alkanoylamino group having
1 to 4 carbon atoms, which may be substituted by a hydroxyl group
or an alkoxy group having 1 to 4 carbon atoms, a phenylamino group,
which may be substituted by a carboxyl, sulfonic or amino group, a
sulfonic group, a halogen atom, or a ureido group, [C] is an
aliphatic amine residue having a carboxyl or sulfonic group, and
M's are, independently of one another, a hydrogen atom, alkali
metal, ammonium or organic ammonium; and
##STR00008## wherein A is an aromatic or heterocyclic group which
may be substituted, B is any one of groups represented by the
following general formulae (1) to (5), and M's are, independently
of each other, a hydrogen atom, alkali metal, ammonium or organic
ammonium,
##STR00009## wherein R.sub.1 to R.sub.9 are, independently of one
another, a hydrogen atom, halogen atom, aliphatic group, aromatic
group, heterocyclic group, carboxyl group, carbamoyl group,
alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic
oxycarbonyl group, acyl group, hydroxyl group, alkoxy group,
aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy
group, carbamoyloxy group, alkoxycarbonyloxy group,
aryloxycarbonyloxy group, amino group, acylamino group, ureido
group, sulfamoylamino group, alkoxycarbonylamino group,
aryloxycarbonylamino group, alkyl- or arylsulfonylamino group,
heterocyclic sulfonylamino group, cyano group, nitro group, alkyl-
or arylthio group, heterocyclic thio group, alkyl- or arylsulfonyl
group, heterocyclic sulfonyl group, alkyl- or arylsulfinyl group,
heterocyclic sulfinyl group, sulfamoyl group, or sulfonic group,
with the proviso that each group may be further substituted.
An ink jet recording method according to a still further embodiment
of the present invention comprises ejecting an ink by an ink jet
system to conduct recording on a recording medium, wherein the ink
is any one ink of the above-described inks.
An ink cartridge according to a yet still further embodiment of the
present invention comprises an ink storage portion for storing an
ink, wherein the ink is any one ink of the above-described
inks.
A recording unit according to a yet still further embodiment of the
present invention comprises an ink storage portion for storing an
ink and a recording head for ejecting the ink, wherein the ink is
any one ink of the above-described inks.
An ink jet recording apparatus according to a yet still further
embodiment of the present invention comprises an ink storage
portion for storing an ink and a recording head for ejecting the
ink, wherein the ink is any one ink of the above-described
inks.
According to the present invention for solving the first problem,
there can be provided an ink having performance required of a gray
ink and being capable of providing an image having ozone fastness
and light fastness on a high level. According to the present
invention for solving the second problem, there can be provided an
ink capable of solving or reducing the problem of metamerism.
According to the present invention for solving the third problem,
there can be provided an ink making combined use of a specific cyan
dye and a specific yellow dye and capable of forming an excellent
image while inhibiting association or aggregation of the cyan dye,
in particular, of a phthalocyanine dye.
According to another embodiment of the present invention in
particular, there is provided an ink capable of providing an image
excellent in ozone fastness and light fastness and having a neutral
gray color tone. According to another embodiment of the present
invention, there are provided an ink jet recording method, an ink
cartridge, a recording unit and an ink jet recording apparatus,
which can provide the above-described excellent image.
Further features of the present invention will become apparent from
the following description of exemplary embodiments with reference
to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an ink jet recording apparatus.
FIG. 2 is a perspective view of a mechanism part of the ink jet
recording apparatus.
FIG. 3 is a sectional view of the ink jet recording apparatus.
FIG. 4 is a perspective view illustrating a state that an ink
cartridge is installed in a head cartridge.
FIG. 5 is an exploded perspective view of the head cartridge.
FIG. 6 is an elevational view illustrating recording element
substrates in the head cartridge.
FIGS. 7A, 7B, 7C, 7D and 7E typically illustrate presence positions
of coloring materials in an ink-receiving layer of a recording
medium when inks containing the respective coloring materials have
been separately applied to the recording medium.
DESCRIPTION OF THE EMBODIMENTS
The present invention will hereinafter be described in detail by
exemplary embodiments. Incidentally, when a compound is a salt, the
salt is present in an ink as being dissociated into ions. In the
present invention, however, the ink is represented as "containing
the salt" for the sake of convenience. In the following
description, the compounds represented by the general formulae (I)
to (VII) may be shortened and described as "compounds of the
general formulae (I) to (VII)", respectively. The number of
substituents in each compound in an ink is an average value unless
expressly noted. The respective embodiments corresponding to the
respective objects in the present invention have been separately
described above. However, the inks may be simply referred to as
"inks according to the present invention". In the following
description, the above-described compounds and coloring materials
may be simply referred to as "first coloring material" and "second
coloring material", and coloring materials and compounds not
included in the present invention may be referred to as "general"
dyes, coloring materials and compounds.
<Ink>
The components making up the ink according to the present invention
and physical properties of the ink will hereinafter be described in
detail.
(Coloring Material)
A main feature of the present invention resides in that a compound
of the following general formula (I) as a first coloring material
and a compound of the following general formula (II) as a second
coloring material are used in combination as coloring materials of
an ink to achieve excellent ozone fastness in an image formed.
[First Coloring Material: Compound Represented by the General
Formula (I)]
The ink according to the present invention requires containing the
compound of the following general formula (I) as the first coloring
material (dye).
##STR00010## wherein A, B, C and D are, independently of one
another, an aromatic six-membered ring, M is a hydrogen atom,
alkali metal, ammonium or organic ammonium, E is an alkylene group,
X is a sulfo-substituted anilino group, carboxyl-substituted
anilino group or phosphono-substituted anilino group, with the
proviso that such a substituted anilino group may further have 1 to
4 substituents selected from the group consisting of sulfonic,
carboxyl, phosphono, sulfamoyl, carbamoyl, hydroxyl, alkoxy, amino,
alkylamino, dialkylamino, arylamino, diarylamino, acetylamino,
ureido, alkyl, nitro, cyano, alkylsulfonyl and alkylthio groups and
halogen atoms, Y is a hydroxyl group or amino group, and l, m and n
have the following relationship: 0.ltoreq.l.ltoreq.2,
0.ltoreq.m.ltoreq.3, 0.1.ltoreq.n.ltoreq.3 and l+m+n=1 to 4.
In the general formula (I), A, B, C and D are, independently of one
another, an aromatic six-membered ring. Examples of the aromatic
six-membered ring include a benzene ring and nitrogen-containing
heterocyclic rings. Examples of the heterocyclic rings include
pyridine, pyrazine, pyrimidine and pyridazine rings. Among these
rings, the pyridine or pyrazine ring is favorable and the pyridine
ring is particularly favorable. Specific examples of the compound
of the general formula (I), which are favorably usable in the
present invention, include the following compounds: compounds in
which all of A, B, C and D are benzene rings or nitrogen-containing
heterocyclic rings, and compounds in which one to three of A, B, C
and D are nitrogen-containing heterocyclic rings and the remainder
is a benzene ring. According to the investigation by the present
inventors, the compound of the general formula (I) has such a
tendency that when the number of nitrogen-containing heterocyclic
rings in the structure thereof increases, the ozone fastness of the
resulting recorded article is improved, while the resistance to
bronzing (inhibition of a bronzing phenomenon) is lowered to the
contrary. Therefore, it is favorable that the number of the
nitrogen-containing heterocyclic rings is controlled in view of a
balance between ozone fastness and resistance to bronzing.
E in the general formula (I) is an alkylene group, and the number
of carbon atoms in the alkylene group is favorably 2 to 12, more
favorably 2 to 6. Specific examples of the alkylene group include
ethylene group, propylene group, butylene group, pentylene group,
hexylene group, cyclopropylenediyl group, 1,2- and
1,3-cyclopentylendiyl groups, and 1,2-, 1,3- and 1,4-cyclohexylene
groups. Among these groups, ethylene, propylene and butylene groups
are favorable.
X in the general formula (I) is a sulfo-substituted anilino group,
carboxyl-substituted anilino group or phosphono-substituted anilino
group. The substituted anilino group may further have 1 to 4
substituents, favorably 1 or 2 substituents selected from the
following substituent group. Substituent group: sulfonic, carboxyl,
phosphono, sulfamoyl, carbamoyl, hydroxyl, alkoxy, amino,
alkylamino, dialkylamino, arylamino, diarylamino, acetylamino,
ureido, alkyl, nitro, cyano, alkylsulfonyl and alkylthio groups and
halogen atoms. Specific examples of X in the general formula (I)
include 2,5-disulfoanilino, 2-sulfoanilino, 3-sulfoanilino,
4-sulfoanilino, 2-carboxyanilino, 2-methoxy-5-sulfoanilino,
4-ethoxy-2-sulfoanilino, 2-methyl-5-sulfoanilino,
2-nitro-4-sulfoanilino, 2-methoxy-4-nitro-5-sulfoanilino,
2-chloro-5-sulfoanilino, 2-carboxy-4-sulfoanilino,
3-carboxy-4-hydroxyanilino, 3-carboxy-4-hydroxy-5-sulfoanilino,
2-hydroxy-5-nitro-3-sulfoanilino, 4-acetylamino-2-sulfoanilino,
4-anilino-3-sulfoanilino, 3,5-dicarboxyanilino,
2-carboxy-4-sulfamoylanilino, 2,5-dichloro-4-sulfoanilino and
3-phosphonoanilino groups.
Y in the general formula (I) is a hydroxyl or amino group.
M in the general formula (I) is a hydrogen atom, alkali metal,
ammonium or organic ammonium. Examples of the alkali metal include
lithium, sodium and potassium. Examples of the organic ammonium
include acetamido, benzamido, methylamino, butylamino, diethylamino
and phenylamino. Incidentally, when the compound of the general
formula (I) has two sulfonic groups, namely 1 in the general
formula (I) is 2, the sulfonic groups may has the same or different
M's.
The sulfonic, carboxyl or phosphono group mentioned upon the
description of X in the compound of the general formula (I) may be
in the form of a salt. Examples of a counter ion for forming the
salt include ions of alkali metals, ammonium and organic ammonium.
Examples of the alkali metals include lithium, sodium and
potassium. Examples of the organic ammonium include onium salts of
alkylamines having 1 to 3 carbon atoms, such as methylamine and
ethylamine, and mono-, di- or tri-[(C1-C4)alkanol]amines such as
monoethanolamine, diethanolamine, triethanolamine,
monoisopropanolamine, diisopropanolamine and triisopropanolamine.
The counter ion may be an alkaline earth metal such as calcium or
magnesium.
The compound of the general formula (I) can be synthesized in the
following manner. A compound (copper porphyrazine compound) of the
following general formula (A) is first synthesized.
##STR00011## wherein A, B, C and D are, independently of one
another, an aromatic six-membered ring.
The compound of the general formula (A) is obtained by, for
example, reacting a nitrogen-containing aromatic heterocyclic
dicarboxylic acid derivative with a phthalic acid derivative in the
presence of a catalyst and a copper compound. The molar ratio in
the reaction of the nitrogen-containing aromatic heterocyclic
dicarboxylic acid derivative with the phthalic acid derivative is
changed, whereby the number of nitrogen-containing aromatic
heterocyclic rings and the number of benzene rings in A, B, C and D
can be controlled.
Examples of the nitrogen-containing aromatic heterocyclic
dicarboxylic acid derivative used at this time include dicarboxylic
acid compounds such as quinolinic acid, 3,4-pyridinedicarboxylic
acid and 2,3-pyrazinedicarboxylic acid, and acid anhydrides
thereof; dicarboxyamide compounds such as
pyridine-2,3-dicarboxyamide; dicarboxylic acid monoamide compounds
such as pyrazine-2,3-dicarboxylic acid monoamide; acid imide
compounds such as quinolinic acid imide; and dicarbonitrile
compounds such as pyridine-2,3-dicarbonitrile and
pyrazine-2,3-dicarbonitrile. Examples of the phthalic acid
derivative include phthalic acid, phthalic anhydride, phthalamide,
phthalamic acid, phthalimide, phthalonitrile,
1,3-diiminoisoindoline and 2-cyanobenzamide.
General methods for synthesizing the copper compound include a
nitrile method and a Wyler's method, which are different from each
other in reaction conditions. The nitrile method is a method for
synthesizing the copper compound by using, as a raw material, a
dicarbonitrile compound such as 2,3-pyridine-dicarbonitrile,
2,3-pyrazine dicarbonitrile or phthalonitrile. The Wyler's method
is a method for synthesizing the copper compound by using the
following compound as a raw material. Examples of the compound
usable as the raw material for the Wyler's method include
dicarboxylic acid compounds such as phthalic acid, quinolinic acid,
3,4-pyridine-dicarboxylic acid, acid and 2,3-pyrazinedicarboxylic
acid, and acid anhydrides thereof; dicarboxyamide compounds such as
phthalimide, 2,3-pyridinedicarboxyamide; dicarboxylic acid
monoamide compounds such as phthalamic acid and
2,3-pyrazinedicarboxylic acid monoamide; and acid imide compounds
such as phthalimide and quinolinic acid imide. Incidentally, urea
is required to synthesize the copper compound by the Wyler's
method, and the amount of urea used is favorably 5 mol to 100 mol
per one mol of the total of the nitrogen-containing aromatic
heterocyclic dicarboxylic acid derivative and phthalic acid
derivative.
The synthesis reaction of the copper compound is generally
conducted in the presence of an organic solvent. In the nitrile
method, an organic solvent having a boiling point of 100.degree. C.
or more, favorably 130.degree. C. or more is used. Examples of
organic solvents usable in the nitrile method include alcohols such
as n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol,
1-heptanol, 1-octanol, 2-ethylhexanol, N,N-dimethyl-aminoethanol
and benzyl alcohol; glycols such as ethylene glycol and propylene
glycol; trichlorobenzene; chloronaphthalene; nitrobenzene;
quinolinesulfolane; and urea. In the Wyler's method, an aprotic
organic solvent having a boiling point of 150.degree. C. or more,
preferably 180.degree. C. or more is used. Examples of organic
solvents usable in the Wyler's method include trichlorobenzene,
chloronaphthalene, nitrobenzene, quinoline, sulfolane and urea. The
amount of the organic solvent used is favorably one to 100 times as
much as the total mass of the nitrogen-containing aromatic
heterocyclic dicarboxylic acid derivative and phthalic acid
derivative.
Examples of catalysts usable in the nitrile method include amines
such as quinoline, 1,8-diazabicyclo[5,5,0]-7-undecene,
tributylamine, ammonia and N,N-dimethylaminoethanol; and alkali
metal alcoholates such as sodium ethoxide and sodium methoxide.
Examples of catalysts usable in the Wyler's method include ammonium
molybdate and boric acid. The amount of these catalysts used is
favorably 0.001 mol to 1 mol per mol of the total of the
nitrogen-containing aromatic heterocyclic dicarboxylic acid
derivative and phthalic acid derivative.
Examples of the copper compound used in the above synthesis include
metal copper, copper halides, copper carboxylates, copper sulfate,
copper nitrate, copper acetylacetonate and copper complexes.
Specifically, copper chloride, copper bromide, copper acetate and
copper acetylacetonate are mentioned. The amount of the copper
compound used is favorably 0.15 mol to 0.35 mol per one mol of the
total of the nitrogen-containing aromatic heterocyclic dicarboxylic
acid derivative and phthalic acid derivative.
The reaction temperature in the nitrile method is favorably
100.degree. C. to 200.degree. C., more favorably 130.degree. C. to
170.degree. C. The reaction temperature in the Wyler's method is
favorably 150.degree. C. to 300.degree. C., more favorably
170.degree. C. to 220.degree. C. Incidentally, the reaction time
varies according to reaction conditions, but is generally favorably
1 hour to 40 hours. After completion of the reaction, filtration,
washing and drying are conducted, whereby the copper porphyrazine
compound represented by the general formula (A) can be
obtained.
A compound (copper dibenzobis(2,3-pyrido)porphyrazine) in which two
of A, B, C and D in the general formula (A) are pyridine rings, and
the remainder are benzene rings is taken as an example to describe
the synthesis process of the compound of the general formula (I) in
more detail.
Quinolinic acid (0.5 mol), phthalic anhydride (0.5 mol), copper(II)
chloride (0.25 mol), phosphorus ammonium molybdate (0.004 mol) and
urea (6 mol) are first reacted for 5 hours at 200.degree. C. in
sulfolane that is an organic solvent. In such a manner, copper
dibenzobis(2,3-pyrido)porphyrazine in which two of A, B, C and D in
the general formula (A) are pyridine rings, and the remainder are
benzene rings is obtained. Incidentally, reactivities of quinolinic
acid, phthalic anhydride, the metal compound, the organic solvent
and the catalyst vary according to the kinds thereof and the
amounts used, and are not limited thereto.
The main product obtained by the above-described synthesis process
is copper dibenzobis(2,3-pyrido)porphyrazine. In this compound, 5
isomers (the following structural formulae 1A, 1B, 1C, 1D and 1E)
that are different in the positions of the pyridine rings and the
positions of the nitrogen atom in the pyridine rings exist. Copper
tribenzo(2,3-pyrido)porphyrazine and copper
benzotris(2,3-pyrido)porphyrazine are formed as by-products at the
same time of the formation of the main product. Copper
tribenzo(2,3-pyrido)porphyrazine is a compound (the following
structural formula 2) in which one of A, B, C and D in the general
formula (A) is a pyridine ring, and the remainder are benzene
rings. Copper benzotris(2,3-pyrido)porphyrazine is a compound in
which three of A, B, C and D in the general formula (A) are
pyridine rings, and the remainder is a benzene ring. In these
compounds, regioisomers (the following structural formulae 3A, 3B,
3C and 3D) with respect to pyridine ring also exist. In addition,
copper tetrakis(2,3-pyrido)porphyrazine and copper phthalocyanine
(copper tetrabenzoporphyrazine) are also formed though the amounts
thereof are small. In other words, the product obtained by the
above-described synthesis process is a mixture of these
compounds.
It is generally very different to isolate only the intended
compound from the mixture of these compounds. Therefore, the
mixture of these compounds is often used as "copper
dibenzobis(2,3-pyrido)porphyrazine in which 2 rings are pyridine
rings and the remainder are benzene rings on the average".
##STR00012## ##STR00013## ##STR00014##
A compound (copper chlorosulfonylporphyrazine compound) of the
following general formula (B) is then synthesized.
##STR00015## wherein A, B, C and D are, independently of one
another, an aromatic six-membered ring, and x is 1 to 4.
The compound of the general formula (B) is obtained by
chlorosulfonating the compound of the general formula (A) obtained
in the above-described manner in chlorosulfonic acid.
The compound is also obtained by sulfonating the compound of the
general formula (A) in a sulfuric acid or fuming sulfuric acid and
then deriving a chlorosulfonic group from the sulfonic group with a
chlorinating agent. When A, B, C and D in the general formula (A)
are benzene rings, the chlorosulfonic group or sulfonic group
obtained in such a manner is introduced into such benzene rings.
When A, B, C and D are nitrogen-containing aromatic heterocyclic
rings, the chlorosulfonic group or sulfonic group is not
introduced. In other words, the chlorosulfonic group or sulfonic
group is introduced into only benzene ring(s) among A, B, C and D
in the general formula (A).
In the reaction for chlorosulfonating the compound of the general
formula (A), chlorosulfonic acid is generally used as a solvent.
The amount of chlorosulfonic acid used is favorably 3 to 20 times,
more favorably 5 to 10 times as much as the mass of the compound of
the general formula (A). The reaction temperature is generally
favorably 100.degree. C. to 150.degree. C., more favorably
120.degree. C. to 150.degree. C. The reaction time varies according
to conditions such as reaction temperature, but is generally
favorably 1 hour to 10 hours. The substituent of the resultant
compound of the general formula (B) is a mixture of the
chlorosulfonic and sulfonic groups. However, the proportion of the
chlorosulfonic group can be increased by adding the chlorinating
agent to the reaction system. Examples of the chlorinating agent
include chlorosulfonic acid, thionyl chloride, sulfuryl chloride,
phosphorus trichloride, phosphorus pentachloride and phosphorus
oxychloride. Needless to say, the present invention is not limited
thereto.
The compound of the general formula (B) can also be obtained by the
following process in addition to the above-described process.
Sulfophthalic acid having a sulfonic group, or sulfophthalic acid
having a sulfonic group and quinolinic acid are subjected to
condensation ring closure, thereby synthesizing a compound (copper
porphyrazine compound having a sulfonic group) of the following
general formula (C). A chlorosulfonic group is derived from the
sulfonic group in the thus-obtained compound of the general formula
(C), whereby the compound of the general formula (B) can be
obtained.
##STR00016## wherein A, B, C and D are, independently of one
another, an aromatic six-membered ring, and p is 1 to 4.
The sulfonic group in the compound of the general formula (C) can
be converted to a chlorosulfonic group by reacting the compound of
the general formula (C) with a chlorinating agent. Examples of a
solvent used in the reaction for the chlorination include sulfuric
acid, fuming sulfuric acid, chlorosulfonic acid, benzene, toluene,
nitrobenzene, chlorobenzene, N,N-dimethylformamide and
N,N-dimethylacetamide. Examples of the chlorinating agent include
chlorosulfonic acid, thionyl chloride, sulfuryl chloride,
phosphorus trichloride, phosphorus pentachloride and phosphorus
oxychloride. Needless to say, the present invention is not limited
thereto.
Finally, the compound of the general formula (B) obtained in the
above-described manner, a compound (organic amine) of the following
general formula (D) and ammonia are reacted to synthesize the
intended compound of the general formula (I).
##STR00017## wherein E is an alkylene group, X is a
sulfo-substituted anilino group, carboxyl-substituted anilino group
or phosphono-substituted anilino group, with the proviso that such
a substituted anilino group may further have 1 to 4 substituents
selected from the group consisting of sulfonic, carboxyl,
phosphono, sulfamoyl, carbamoyl, hydroxyl, alkoxy, amino,
alkylamino, dialkylamino, arylamino, diarylamino, acetylamino,
ureido, alkyl, nitro, cyano, alkylsulfonyl and alkylthio groups and
halogen atoms, and Y is a hydroxyl group or amino group.
Specifically, the compound of the general formula (I) used in the
present invention can be synthesized by using the above-described
respective compounds according to the following procedure. Namely,
the compound of the general formula (B) obtained above, the
compound of the general formula (D) and ammonia (aminating agent)
are reacted for 1 hour to 20 hours under conditions of generally a
pH of 8 to 10 and a temperature of 5.degree. C. to 70.degree. C.,
thereby obtaining the compound of the general formula (I). Examples
of ammonia used at this time include ammonium salts such as
ammonium chloride and ammonium sulfate, urea, aqueous ammonia, and
ammonia gas. The use of these compounds permits introducing them
into the reaction system. Incidentally, the reaction of the
compound of the general formula (B), the compound of the general
formula (C) and the aminating agent is generally conducted in
water. The amount of mole of the compound of the general formula
(D) is favorably 1 times or more the theoretical value per one mol
of the compound of the general formula (B) though the amount varies
according to the reactivity of the compound of the general formula
(D) and reaction conditions.
The compound of the general formula (D) can be synthesized in the
following manner. A substituted aniline compound (0.95 to 1.0 mol)
corresponding to X in the general formula (D) and
2,4,6-trichloro-S-triazine (cyanuric chloride, 1 mol) are first
reacted for 2 hours to 12 hours under conditions of a pH of 3 to 7
and a temperature of 5.degree. C. to 40.degree. C. in water,
thereby obtaining a primary condensate. When the compound of the
general formula (D), in which Y in the formula is an amino group,
is provided, the primary condensate obtained above is then reacted
with ammonia (0.95 to 2.0 mol) for 0.5 to 12 hours under conditions
of a pH of 4 to 10 and a temperature of 5.degree. C. to 80.degree.
C. When the compound of the general formula (D), in which Y in the
formula is a hydroxyl group, is provided, an alkali metal hydroxide
such as sodium hydroxide is then added to the primary condensate
obtained above to conduct a reaction for 0.5 to 8 hours under
conditions of a pH of 4 to 10 and a temperature of 5.degree. C. to
80.degree. C. The compound of the general formula (D) can be
obtained according to such procedure. Incidentally, the pH upon the
condensation can be adjusted with an alkali metal hydroxide such as
sodium hydroxide or potassium hydroxide, or an alkali metal
carbonate such as sodium carbonate or potassium carbonate.
Incidentally, the order of the condensation can be suitably
determined according to the reactivity of the respective
compound.
As described above, the compound of the general formula (I) is
synthesized from the compound of the general formula (B) and the
compound of the general formula (D) in the presence of ammonia.
Therefore, it is considered that a part of the chlorosulfonyl group
in the compound of the general formula (B) is theoretically
hydrolyzed with water present in the reaction system to form a
product converted to sulfonic acid as a by-product and the
by-product is mixed into the compound of the general formula (I).
However, it is difficult to distinguish an unsubstituted sulfamoyl
group from a sulfonic group by mass spectrometric analysis. In the
present invention, all chlorosulfonyl groups in other compounds of
the general formula (B) than that reacted with the compound
(organic amine) of the general formula (D) are thus described as
those converted to an unsubstituted sulfamoyl group
(--SO.sub.2--NH.sub.2).
When the compound of the general formula (I) is synthesized
according to the above-described process, impurities resulting from
the reaction in which a copper porphyrazine ring (Pz) forms a dimer
(Pz-L-Pz) and a trimer (Pz-L-Pz-L-Pz) through a divalent linking
group may be mixed as by-products in the reaction product in some
cases. In this case, the divalent linking group (L) is --SO.sub.2--
or --SO.sub.2--NH--SO.sub.2--. In the case of the trimer, these 2
linking groups (L) may be combined in some cases to form the
by-product.
The compound of the general formula (I) can be taken out of such
reaction system as described above by filtration after conducting
acidifying out or salting out. The salting out can be conducted in
an acidic to alkaline range and is favorably conducted in a pH
range of from 1 to 11. The salting out is favorably conducted by
heating the reaction product to 40 to 80.degree. C., favorably 50
to 70.degree. C. and then adding common salt.
The compound of the general formula (I) synthesized by such process
as described above is provided in the form of a free acid or a salt
thereof. In order to provide the compound of the general formula
(I) in the form of the free acid, it is only necessary to conduct
acidifying out. In order to provide the compound of the general
formula (I) in the form of the salt, it is only necessary to
conduct salting out. If the desired salt is not provided by the
salting out, it is only necessary to utilize, for example, an
ordinary salt interchange method in which the reaction product is
converted to the form of a free acid, and a desired organic or
inorganic base is then added.
Specific favorable examples of the compound of the general formula
(I) include Exemplified Compounds I-1 to I-25 shown in the
following Table 1. Incidentally, in Table 1, portions of A, B, C,
D, E, X and Y in the general formula (I) are respectively shown.
Needless to say, the compounds of the general formula (I) in the
present invention are not limited to the following Exemplified
Compounds so far as the compounds are embraced in the structure of
the general formula (I) and definition thereof. When A, B, C and D
in the general formula (I) are pyridine rings, regioisomers with
respect to the nitrogen atom exist as described above, and so a
mixture of these regioisomers is contained upon the synthesis of
the compound. It is difficult to isolate these isomers, and it is
also difficult to identify these isomer by analysis. Accordingly,
the compound of the general formula (I) is generally used in the
form of the mixture. However, the effects of the present invention
are achieved even when containing isomers, so that the compound of
the general formula (I) is described herein without distinguishing
the isomers. In the present invention, the number of pyridine rings
among A, B, C and D in the general formula (I) is favorably 1 to 3,
more favorably 1 or 2. In this case, an image having better ozone
fastness can be achieved, and an absorption wavelength becomes
broad, so that a color difference due to difference in light source
becomes low, and metamerism is improved. Among the following
Exemplified Compounds, Exemplified Compounds I-1 to I-3, I-10 to
I-12, I-21 to I-23, and I-25 are particularly favorably used.
Incidentally, Exemplified Compound I-25 is a compound of M in the
general formula (I) corresponds to sodium.
TABLE-US-00001 TABLE 1 Exemplified Compounds of general formula (I)
Exemplified Compound A B C D E X Y l m n I-1 2,3-PD Bz Bz Bz Et
2,5-Disulfoanilino NH.sub.2 0 2 1 I-2 2,3-PD 2,3-PD Bz Bz Et
2,5-Disulfoanilino NH.sub.2 0 1 1 I-3 2,3-PD Bz 2,3-PD Bz Et
2,5-Disulfoanilino NH.sub.2 0 1 1 I-4 2,3-PD 2,3-PD 2,3-PD Bz Et
2,5-Disulfoanilino NH.sub.2 0 0 1 I-5 2,3-PD Bz Bz Bz Et
4-Sulfoanilino NH.sub.2 0 2 1 I-6 2,3-PD Bz Bz Bz Et
2,5-Disulfoanilino OH 0 2 1 I-7 2,3-PD Bz Bz Bz Et
3,5-Dicarboxyanilino NH.sub.2 0 2 1 I-8 2,3-PD Bz Bz Bz Pr
2,5-Disulfoanilino NH.sub.2 0 2 1 I-9 2,3-PD Bz Bz Bz Et
2-Carboxy-4-sulfoanilino NH.sub.2 0 2 1 I-10 2,3-PZ Bz Bz Bz Et
2,5-Disulfoanilino NH.sub.2 0 2 1 I-11 2,3-PZ 2,3-PZ Bz Bz Et
2,5-Disulfoanilino NH.sub.2 0 1 1 I-12 2,3-PZ Bz 2,3-PZ Bz Et
2,5-Disulfoanilino NH.sub.2 0 1 1 I-13 2,3-PZ 2,3-PZ 2,3-PZ Bz Et
2,5-Disulfoanilino NH.sub.2 0 0 1 2,3-PD: 2,3-Pyrido 2,3-PZ:
2,3-Pyrazino Bz: Benzo Et: Ethylene Pr: Propylene. I-14 2,3-PD Bz
Bz Bz Et 2-Metoxy-5-sulfoanilino NH.sub.2 0 2 1 I-15 2,3-PD Bz Bz
Bz Et 2-Nitro-4-sulfoanilino NH.sub.2 0 2 1 I-16 2,3-PD Bz Bz Bz Et
2,5-Dichloro-4-sulfoanilino NH.sub.2 0 2 1 I-17 2,3-PD Bz Bz Bz Bt
2,5-Disulfoanilino NH.sub.2 0 2 1 I-18 2,3-PD Bz Bz Bz Et
3-Carboxy-4-hydroxy-5-sulfoanilino NH.sub.2 0 2 1 I-19 2,3-PD Bz Bz
Bz Et 2-Sulfoanilino OH 0 2 1 I-20 2,3-PD Bz Bz Bz Et
3-Sulfoanilino OH 0 2 1 I-21 3,4-PD Bz Bz Bz Et 2,5-Disulfoanilino
NH.sub.2 0 2 1 I-22 3,4-PD 3,4-PD Bz Bz Et 2,5-Disulfoanilino
NH.sub.2 0 1 1 I-23 3,4-PD Bz 3,4-PD Bz Et 2,5-Disulfoanilino
NH.sub.2 0 1 1 I-24 3,4-PD 3,4-PD 3,4-PD Bz Et 2,5-Disulfoanilino
NH.sub.2 0 0 1 I-25 Bz Bz Bz Bz Et 2,5-Disulfoanilino NH.sub.2 1 2
1 2,3-PD: 2,3-Pyrido 3,4-PD: 3,4-Pyrido Bz: Benzo Et: Ethylene Bt:
Butylene.
[Second Coloring Material: Compound Represented by the General
Formula (II)]
The ink according to the present invention requires containing the
compound represented by the following general formula (II) as the
second coloring material (dye) together with the above-described
first coloring material.
##STR00018## wherein R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2 are,
independently of one another, a monovalent group, X.sub.1 and
X.sub.2 are, independently of each other, an electron attractive
group having a Hammett's .sigma.p value of 0.20 or more, Z.sub.1
and Z.sub.2 are, independently of each other, a hydrogen atom,
substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl
group, substituted or unsubstituted aralkyl group, substituted or
unsubstituted aryl group, or substituted or unsubstituted
heterocyclic group, and M is a hydrogen atom, alkali metal,
ammonium or organic ammonium.
R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2 in the general formula (II)
are, independently of one another, a monovalent group.
Specifically, the monovalent group may be the following
substituent: hydrogen atom, halogen atom, alkyl, cycloalkyl,
aralkyl, alkenyl, alkynyl, aryl, heterocyclic, cyano, hydroxyl,
nitro, alkoxy, aryloxy, silyloxy, heterocyclic oxy, acyloxy,
carbomoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy,
amino(alkylamino, arylamino), acylamino(amido),
aminocarbonylamino(ureido), alkoxycarbonylamino,
aryloxycarbonylamino, sulfamoylamino, alkylsulfonylamino,
arylsulfonylamino, alkylthio, arylthio, heterocyclic thio,
sulfamoyl, alkylsulfinyl, arylsulfonyl, alkylsulfonyl,
arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl,
phosphino, phosphinyl, phosphinylamino, silyl, azo or imido group.
These groups may be further substituted.
Among the above-mentioned substituents, the monovalent group is
favorably the following substituent: hydrogen atom, halogen atom,
alkyl, aryl, heterocyclic, cyano, alkoxy, amido, ureido,
alkylsulfonylamino, arylsulfonylamino, sulfamoyl, alkylsulfonyl,
arylsulfonyl, carbamoyl or alkoxycarbonyl group. Among these
substituents, hydrogen atom, halogen atom, alkyl, aryl, cyano,
alkylsulfonyl, arylsulfonyl and heterocyclic groups are
particularly favorable.
R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2 in the general formula (II)
will hereinafter be described in more detail.
Examples of the halogen atom include chlorine, bromine and iodine
atoms. Among these, the chlorine or bromine atom is favorable, and
the chlorine atom is particularly favorable.
Examples of the alkyl group include substituted or unsubstituted
alkyl groups having 1 to 30 carbon atoms. Specific examples thereof
include methyl, ethyl, butyl, t-butyl, n-octyl, eicosyl,
2-chloroethyl, hydroxyethyl, cyanoethyl and 4-sulfobutyl.
Examples of the cycloalkyl group include substituted or
unsubstituted cycloalkyl groups having 5 to 30 carbon atoms.
Specific examples thereof include cyclohexyl, cyclopentyl and
4-n-dodocylcyclohexyl.
Examples of the aralkyl group include substituted or unsubstituted
aralkyl groups having 7 to 30 carbon atoms. Specific examples
thereof include benzyl and 2-phenethyl.
Examples of the alkenyl group include substituted or unsubstituted
alkenyl groups having 2 to 30 carbon atoms. Specific examples
thereof include vinyl, allyl, prenyl, geranyl, oleyl,
2-cyclopenten-1-yl and 2-cyclohexen-1-yl.
Examples of the alkynyl group include substituted or unsubstituted
alkynyl groups having 2 to 30 carbon atoms. Specific examples
thereof include ethynyl and propargyl.
Examples of the aryl group include substituted or unsubstituted
aryl groups having 6 to 20 carbon atoms. Specific examples thereof
include phenyl, p-tolyl, naphthyl, m-chlorophenyl and
o-hexadecanoylaminophenyl.
The heterocyclic group is a five-membered or six-membered ring and
is a monovalent group obtained by removing a hydrogen atom from a
substituted or unsubstituted aromatic or non-aromatic heterocyclic
compound. This heterocyclic group may be further fused. In
particular, the heterocyclic group is favorably a five-membered or
six-membered aromatic heterocyclic group having 3 to 50 carbon
atoms. When examples of the heterocyclic group are mentioned
without limiting a substituted position, examples thereof include
pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline,
isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline,
pyrrole, indole, furan, benzofuran, thiophene, benzothiophene,
pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole,
thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole,
isoxazole, benzisoxazole, pyrrolidone, piperidine, piperazine,
imidazolidine and thiazoline.
Examples of the alkoxy group include substituted or unsubstituted
alkoxy groups having 1 to 30 carbon atoms. Specific examples
thereof include methoxy, ethoxy, isopropoxy, n-octyloxy,
methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.
Examples of the aryloxy group include substituted or unsubstituted
aryloxy groups having 6 to 30 carbon atoms. Specific examples
thereof include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy,
3-nitro-phenoxy and 2-tetradecanoylaminophenoxy.
Examples of the silyloxy group include silyloxy groups having 3 to
30 carbon atoms. Specific examples thereof include
trimethylsilyloxy and t-butyldimethylsilyloxy.
Examples of the heterocyclic oxy group include substituted or
unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms.
Specific examples thereof include 1-phenyltetrazole-5-oxy and
2-tetrahydropyranyloxy.
Examples of the acyloxy group include substituted or unsubstituted
alkylcarbonyloxy groups having 2 to 30 carbon atoms and substituted
or unsubstituted arylcarbonyloxy groups having 6 to 30 carbon
atoms. Specific examples thereof include formyloxy, acetyloxy,
pivaloyloxy, stearoyloxy, benzoyloxy and
p-methoxyphenylcarbonyloxy.
Examples of the carbamoyloxy group include substituted or
unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms.
Specific examples thereof include N,N-dimethylcarbamoyloxy,
N,N-diethylcarbamoyl-oxy, morpholinocarbonyloxy,
N,N-di-n-octylaminocarbonyloxy and N-n-octylcarbamoyloxy.
Examples of the alkoxycarbonyloxy group include substituted or
unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms.
Specific examples thereof include methoxycarbonyloxy,
ethoxycarbonyloxy, t-butoxycarbonyloxy and
n-octyloxycarbonyloxy.
Examples of the aryloxycarbonyloxy group include substituted or
unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon
atoms. Specific examples thereof include phenoxycarbonyloxy,
p-methoxyphenoxy-carbonyloxy and
p-n-hexadecyloxyphenoxycarbonyloxy.
Examples of the amino group include substituted or unsubstituted
alkylamino groups having 1 to 30 carbon atoms and substituted or
unsubstituted arylamino groups having 6 to 30 carbon atoms.
Specific examples thereof include amino, methylamino,
dimethylamino, anilino, N-methylanilino, diphenylamino,
hydroxyethylamino, carboxyethylamino, sulfoethylamino and
3,5-dicarboxyanilino.
Examples of the acylamino group include substituted or
unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms
and substituted or unsubstituted arylcarbonylamino groups having 6
to 30 carbon atoms. Specific examples thereof include formylamino,
acetylamino, pivaloylamino, lauroylamino, benzoylamino and
3,4,5-tri-n-octyloxyphenylcarbonyl-amino.
Examples of the aminocarbonylamino group include substituted or
unsubstituted aminocarbonylamino groups having 1 to 30 carbon
atoms. Specific examples thereof include carbamoylamino,
N,N-dimethylamono-carbonylamino, N,N-diethylaminocarbonylamino and
morpholinecarbonylamino.
Examples of the alkoxycarbonylamino group include substituted or
unsubstituted alkoxycarbonyl-amino groups having 2 to 30 carbon
atoms. Specific examples thereof include methoxycarbonylamino,
ethoxy-carbonylamino, t-butoxycarbonylamino,
n-octadecyloxy-carbonylamino and N-methyl-methoxycarbonylamino.
Examples of the aryloxycarbonylamino group include substituted or
unsubstituted aryloxycarbonyl-amino groups having 7 to 30 carbon
atoms. Specific examples thereof include phenoxycarbonylamino,
p-chlorophenoxycarbonylamino and
m-n-octyloxyphenoxy-carbonylamino.
Examples of the sulfamoylamino group include substituted or
unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms.
Specific examples thereof include sulfamoylamino,
N,N-dimethylaminosulfonylamino and N-n-octylaminosulfonylamino.
Examples of the alkylsulfonylamino group and arylsulfonylamino
group include substituted or unsubstituted alkylsulfonylamino
groups having 1 to 30 carbon atoms and substituted or unsubstituted
arylsulfonylamino groups having 6 to 30 carbon atoms. Specific
examples thereof methylsulfonylamino, butylsulfonylamino,
phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino and
p-methylphenylsulfonylamino.
Examples of the alkylthio group include substituted or
unsubstituted alkylthio groups having 1 to 30 carbon atoms.
Specific examples thereof methylthio, ethylthio and
n-hexadecylthio.
Examples of the arylthio group include substituted or unsubstituted
arylthio groups having 6 to 30 carbon atoms. Specific examples
thereof include phenylthio, p-chlorophenylthio and
m-methoxyphenylthio.
Examples of the heterocyclic thio group include substituted or
unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms.
Specific examples thereof include 2-benzothiazolylthio and
1-phenyltetrazol-5-ylthio.
Examples of the sulfamoyl group include substituted or
unsubstituted sulfamoyl groups having 0 to 30 carbon atoms.
Specific examples thereof include N-ethylsulfamoyl,
N-(3-dodecyloxypropyl)sulfamoyl, N,N-dimethylsulfamoyl,
N-acetylsulfamoyl, N-benzoyl-sulfamoyl and
N--(N'-phenylcarbamoyl)sulfamoyl.
Examples of the alkylsulfinyl group and aryl-sulfinyl group include
substituted or unsubstituted alkylsulfinyl groups having 1 to 30
carbon atoms and substituted or unsubstituted arylsulfonyl groups
having 6 to 30 carbon atoms. Specific examples thereof include
methylsulfinyl, ethylsulfinyl, phenylsulfinyl and
p-methylphenylsulfinyl.
Examples of the alkylsulfonyl group and arylsulfonyl group include
substituted or unsubstituted alkylsulfonyl groups having 1 to 30
carbon atoms and substituted or unsubstituted arylsulfonyl groups
having 6 to 30 carbon atoms. Specific examples thereof include
methylsulfonyl, ethylsulfonyl, phenylsulfonyl and
p-toluenesulfonyl.
Examples of the acyl group include formyl, substituted or
unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms,
substituted or unsubstituted arylcarbonyl groups having 7 to 30
carbon atoms, and substituted or unsubstituted heterocyclic
carbonyl groups having 4 to 30 carbon atoms and bonded to a
carbonyl group through a carbon atom. Specific examples thereof
include acetyl, pivaloyl, 2-chloro-acetyl, stearoyl, benzoyl,
p-n-octyloxyphenylcarbonyl, 2-pyridinecarbonyl and
2-furylcarbonyl.
Examples of the aryloxycarbonyl group include substituted or
unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms.
Specific examples thereof include phenoxycarbonyl,
o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl and
p-t-butylphenoxycarbonyl.
Examples of the alkoxycarbonyl group include substituted or
unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms.
Specific examples thereof include methoxycarbonyl, ethoxycarbonyl,
t-butoxycarbonyl and n-octadecyloxycarbonyl.
Examples of the carbamoyl group include substituted or
unsubstituted carbamoyl groups having 1 to 30 carbon atoms.
Specific examples thereof include carbamoyl, N-methylcarbamoyl,
N,N-dimethylcarbamoyl, N,N-di-n-octylcarbamoyl and
N-(methylsulfonyl)carbamoyl.
Examples of the phosphino group include substituted or
unsubstituted phosphino groups having 2 to 30 carbon atoms.
Specific examples thereof include dimethylphosphino,
diphenylphosphino and methylphenoxy-phosphino.
Examples of the phosphinyl group include substituted or
unsubstituted phosphinyl groups having 2 to 30 carbon atoms.
Specific examples thereof include phosphinyl, dioctyloxyphosphinyl
and diethoxyphosphinyl.
Examples of the phosphinyloxy group include substituted or
unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms.
Specific examples thereof include diphenoxyphosphinyloxy and
dioctyloxyphosphinyloxy.
Examples of the phosphinylamino group include substituted or
unsubstituted phosphinylamino groups having 2 to 30 carbon atoms.
Specific examples thereof include dimethoxyphosphinylamino and
dimethylamino-phosphinylamino.
Examples of the silyl group include substituted or unsubstituted
silyl groups having 3 to 30 carbon atoms. Specific examples thereof
include trimethylsilyl, t-butyldimethylsilyl and
phenyldimethylsilyl.
Specific examples of the azo group include phenylazo,
4-methoxyphenylazo, 4-pivaloylaminophenylazo and
2-hydroxy-4-propanoylphenylazo.
Specific examples of the imido group include N-succinimido and
N-phthalimido.
These substituents may be further substituted. Examples of
substituents in this case include the following substituents:
linear or branched alkyl groups having 1 to 12 carbon atoms, linear
or branched aralkyl groups having 7 to 18 carbon atoms, linear or
branched alkenyl groups having 2 to 12 carbon atoms, linear or
branched alkynyl groups having 2 to 12 carbon atoms, linear or
branched cycloalkyl groups having 3 to 12 carbon atoms and linear
or branched cycloalkenyl groups having 3 to 12 carbon atoms. These
substituents favorably have a branched chain and more favorably
have an asymmetric carbon atom for the purpose of improving the
solubility of the dye used and the stability of the resulting
ink.
As specific examples of the substituents, may be mentioned the
following substituents: substituted or unsubstituted alkyl groups
such as methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl,
2-ethylhexyl, 2-methylsulfoethyl, 3-phenoxypropyl, trifluoromethyl
and cyclopentyl; halogen atoms such as chlorine and bromine atoms;
aryl groups such as phenyl, 4-t-butylphenyl and
2,4-di-t-amylphenyl; heterocyclic groups such as imidazolyl,
pirazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl and
2-benzothiazolyl; cyano group; hydroxyl group; nitro group,
carboxyl group; amino group; alkyloxy groups such as methoxy,
ethoxy, 2-methoxyethoxy and 2-methylsulfonylethoxy; aryloxy groups
such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy,
3-t-butylcarbonylphenoxy and 3-methoxycarbonylphenyloxy; acylamino
groups such as acetamido, benzamido and
4-(3-t-butyl-4-hydroxyphenoxy)butanamido; alkylamino groups such as
methylamino, butylamino, diethylamino and methylbutylamino; anilino
groups such as phenylamino and 2-chloroanilino; ureido groups such
as phenylureido, methylureido and N,N-dibutylureido; sulfamoylamino
groups such as N,N-dipropylsulfamoylamino; alkylthio groups such as
methylthio, octylthio and 2-phenoxy-ethylthio; arylthio groups such
as phenylthio, 2-butoxy-5-t-octylphenylthio and
2-carboxyphenylthio; alkyloxycarbonylamino groups such as
methoxycarbonylamino; alkyl- or arylsulfonylamino groups such as
methylsulfonylamino, phenylsulfonylamino and
p-toluenesulfonylamino; carbamoyl groups such as N-ethylcarbamoyl
and N,N-dibutylcarbamoyl; sulfamoyl groups such as
N-ethylsulfamoyl, N,N-dipropylsulfamoyl and N-phenylsulfamoyl;
sulfonyl groups such as methyl-sulfonyl, octylsulfonyl,
phenylsulfonyl and p-toluene-sulfonyl; alkyloxycarbonyl groups such
as methoxy-carbonyl and butyloxycarbonyl; heterocyclic oxy groups
such as 1-phenyltetrazol-5-oxy and 2-tetrahydropyranyloxy; azo
groups such as phenylazo, 4-methoxyphenylazo,
4-pivaloylaminophenylazo and 2-hydroxy-4-propanoyl-phenylazo;
acyloxy groups such a acetoxy; carbamoyloxy groups such as
N-methylcarbamoyloxy and N-phenyl-carbamoyloxy; silyloxy groups
such as trimethylsilyloxy and dibutylmethylsilyloxy;
aryloxycarbonylamino groups such as phenoxycarbonylamino; imido
groups such as N-succinimido and N-phthalimido; heterocyclic thio
groups such as 2-benzothiazolylthio,
2,4-diphenoxy-1,3,5-triazol-6-thio and 2-pyridylthio; sulfinyl
groups such as 3-phenoxypropylsulfinyl; phosphonyl groups such as
phenoxyphosphonyl, octylphosphonyl and phenyl-phosphonyl;
aryloxycarbonyl groups such as phenoxy-carbonyl; acyl groups such
as acetyl, 3-phenylpropanoyl and benzoyl; and ionic hydrophilic
groups such as carboxyl, sulfonic, phosphono and quaternary
ammonium groups.
The second coloring material used in the present invention and
represented by the general formula (II) requires that X.sub.1 and
X.sub.2 in the general formula (II) are, independently of each
other, an electron attractive group having a Hammett's .sigma.p
value of 0.20 or more. Here, Hammett's rule and Hammett's
substituent constant, .sigma.p value (hereinafter referred to as
"Hammett's .sigma.p value") will now be described. The Hammett's
rule is an empirical rule advocated by L. P. Hammett in 1935 for
quantitatively discussing the influence of a substituent on the
reaction and equilibrium of a benzene derivative and its propriety
is widely recognized at present. The substituent constants
determined by the Hammett's role include a .sigma.p value and a
.sigma.m value. These values are set forth in many general books.
For example, the detailed description thereof is given in Langer's
Handbook of Chemistry, 12.sup.th edition; edited by J. A. Dean,
1979, McGraw-Hill, and Region of Chemistry, extra edition; No. 122,
pp. 96 to 103, 1979, Nanko-do.
In the present invention, the respective substituents are defined
by the Hammett's .sigma.p value. However, the present invention is
not limited to substituents whose .sigma.p values were specifically
described in such literature as described above. It is needless to
say that the present invention also includes substituents whose
.sigma.p values are not described in such literature as described
above but are to be included within the range when the .sigma.p
values thereof are calculated out according to the Hammett's rule.
The compound of the general formula (II) is not a benzene
derivative. In the present invention, however, the .sigma.p value
is used as a scale indicating the electron effect of a substituent
irrespective of the substituted position. Specific examples of
substituents usable as electron attractive groups having a
Hammett's .sigma.p value of 0.20 or more in the substituents that
the compound of the general formula (II) used in the present
invention has will hereinafter be mentioned in terms of range of
the Hammett's .sigma.p value.
Electron attractive groups having a Hammett's .sigma.p value of
0.60 or more include the following groups: cyano, nitro,
alkylsulfonyl (for example, methane-sulfonyl) and arylsulfonyl (for
example, benzene-sulfonyl) groups.
Electron attractive groups having a Hammett's .sigma.p value of
0.45 or more include, in addition to the above-mentioned groups,
the following groups: acyl (for example, acetyl), alkoxycarbonyl
(for example, dodecyloxycarbonyl), aryloxycarbonyl (for example,
m-chlorophenoxycarbonyl), alkylsulfinyl (for example,
n-propylsulfinyl), arylsulfinyl (for example, phenylsulfinyl),
sulfamoyl (for example, N-ethyl-sulfamoyl, N,N-dimethylsulfamoyl)
and halogenated alkyl (for example, trifluoromethyl) groups.
Electron attractive groups having a Hammett's .sigma.p value of
0.30 or more include, in addition to the above-mentioned groups,
the following groups: acryoxy (for example, acetoxy), carbamoyl
(for example, N-ethylcarbamoyl, N,N-dibutylcarbamoyl), halogenated
alkoxy (for example, trifluoromethyloxy), halogenated aryloxy (for
example, pentafluorophenyloxy), sulfonyloxy (for example,
methylsulfonyloxy), halogenated alkylthio (for example,
difluoromethylthio), aryl substituted with 2 or more substituents
having a .sigma.p value of 0.15 or more (for example,
2,4-dinitrophenyl, pentafluorophenyl), and heterocyclic (for
example, 2-benzoxazolyl, 2-benzothiazolyl,
1-phenyl-2-benzimidazole).
Electron attractive groups having a Hammett's .sigma.p value of
0.20 or more include halogen atoms (for example, fluorine,
chlorine, bromine) in addition to the above-mentioned groups.
Z.sub.1 and Z.sub.2 in the general formula (II) are, independently
of each other, any one of the following substituents: hydrogen
atom, substituted or unsubstituted alkyl group, substituted or
unsubstituted alkenyl group, substituted or unsubstituted alkynyl
group, substituted or unsubstituted aralkyl group, substituted or
unsubstituted aryl group, and substituted or unsubstituted
heterocyclic group. Examples of the alkyl group include the same
groups as the alkyl groups mentioned above in the description of
R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2. Examples of the alkenyl
group include the same groups as the alkenyl groups mentioned above
in the description of R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2.
Examples of the alkynyl group include the same groups as the
alkynyl groups mentioned above in the description of R.sub.1,
R.sub.2, Y.sub.1 and Y.sub.2. Examples of the aralkyl group include
the same groups as the aralkyl groups mentioned above in the
description of R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2. Examples of
the aryl group include the same groups as the aryl groups mentioned
above in the description of R.sub.1, R.sub.2, Y.sub.1 and Y.sub.2.
Examples of the heterocyclic group include the same groups as the
heterocyclic groups mentioned above in the description of R.sub.1,
R.sub.2, Y.sub.1 and Y.sub.2. These substituents may be further
substituted. Examples of substituents in this case include the same
groups as the groups for further substituting the substituents
mentioned above in the description of R.sub.1, R.sub.2, Y.sub.1 and
Y.sub.2.
M in the general formula (II) is a hydrogen atom, alkali metal,
ammonium or organic ammonium. Examples of the alkali metal include
lithium, sodium and potassium. Examples of the organic ammonium
include acetamido, benzamido, methylamino, butylamino, diethylamino
and phenylamino.
Specific favorable examples of the compound of the general formula
(II) include the following Exemplified Compounds II-1 to II-14.
Incidentally, the following Exemplified Compounds are described in
the form of a free acid. Needless to say, the compounds of the
general formula (II) in the present invention are not limited to
the following Exemplified Compounds so far as the compounds are
embraced in the structure of the general formula (II) and
definition thereof. Among the following Exemplified Compounds,
Exemplified Compounds II-5, II-6, II-7, II-8 and II-10 are
favorably used in the present invention.
##STR00019## ##STR00020## ##STR00021## ##STR00022##
[Contents of First Coloring Material and Second Coloring
Material]
The content (% by mass) of the first coloring material (compound of
the general formula (I)) in the ink is favorably from 0.1% by mass
or more to 10.0% by mass or less based on the total mass of the
ink. The content (% by mass) of the second coloring material
(compound of the general formula (II)) in the ink is favorably from
0.1% by mass or more to 10.0% by mass or less based on the total
mass of the ink.
The total of the content (% by mass) of the first coloring material
and the content (% by mass) of the second coloring material in the
ink is favorably from 1.0% by mass or more to 10.0% by mass or less
based on the total mass of the ink. The total of the content (% by
mass) of these coloring materials is particularly favorably from
1.5% by mass or more to 7.0% by mass or less. If the total of the
content is less than 1.0% by mass, the ozone fastness and color
develop abilities of the resulting image may not be sufficiently
achieved in some cases. If the total of the content exceeds 10.0%
by mass, the ink jet properties such as sticking resistance may not
be achieved in some cases.
The content (% by mass) of the first coloring material based on the
total mass of the ink is favorably from 0.1 times or more to 15.0
times or less in terms of mass ratio to the content (% by mass) of
the second coloring material (first coloring material/second
coloring material). More specifically, the ratio {the content of
the compound of the general formula (I)/the content of the compound
of the general formula (II)} is favorably from 0.1 times or more to
15.0 times or less. When the mass ratio between these contents is
controlled within the above range, the ozone fastness of the
resulting image can be particularly improved. In the present
invention, the mass ratio is more favorably from 1.0 time or more
to 8.0 times or less. When the mass ratio between these contents is
controlled within the above range, the interaction (which will be
described in detail subsequently) between the first coloring
material and the second coloring material is particularly strongly
exhibited, whereby better ozone fastness of the image can be
achieved.
[Investigation on the Effect to Improve the Ozone Fastness of an
Image by the Combined Use of First Coloring Material and Second
Coloring Material]
As described above, in an image formed with the ink containing the
second coloring material excellent in the ozone fastness and light
fastness of the resulting image, and the first coloring material,
the marked lowering of ozone fastness in an image formed with a
conventional ink due to marked deterioration of a cyan component
was inhibited. This result can be explained from the relative
relation between the first coloring material and the second
coloring material in the ink and analysis of the image formed.
The present inventors have carried out an investigation on the
image formed with the ink according to the present invention, and
images formed with inks making combined use of other coloring
materials or inks making single use of the respective coloring
materials as follows. Specifically, the position of each coloring
material in a thickness-wise direction of an ink-receiving layer of
a recording medium (permeation depth) was measured by cutting each
image and observing the section thereof, and the positions measured
were compared. As a result, the position of each coloring material
existing in the ink-receiving layer was similar between the image
formed with the ink containing only a general cyan dye and the
image formed with the ink containing the general cyan dye and the
compound of the general formula (II). In other words, the existing
position of the general cyan dye was concentrated in the vicinity
of the surface of the ink-receiving layer and was at a shallow
position in the thickness-wise direction. On the other hand, in the
image formed with the ink containing the compound of the general
formula (I) and the compound of the general formula (II), the
compound of the general formula (I) permeated into the
ink-receiving layer of the recording medium and existed
dispersively up to a position relatively deep from the surface.
Namely, it has been found that the ink containing the first
coloring material and second coloring material makes the first
coloring material permeate and exist at a deeper position than the
conventional ink.
The present inventors have analyzed the condition of dyes in inks
and searched the aggregation condition or association condition of
the dyes in the inks and the adsorption rates of the respective
dyes on components making up an ink-receiving layer. Incidentally,
upon the search of the adsorption rates, alumina hydrate and silica
particles that are general as the components making up the
ink-receiving layer have been investigated.
<Aggregation Condition or Association Condition of Dye in
Ink>
The aggregation condition or association condition of a dye can be
determined by a small angle X-ray scattering method. The small
angle X-ray scattering method is a method commonly used in
calculation of an interparticle distance in a colloidal solution as
described in "New Colloidal Chemistry" (KODANSHA SCIENTIFIC LTD.,
KITAHARA Fumio, FURUSAWA Kunio), and "Surface State and Colloidal
State" (TOKYO KAGAKU DOZIN CO., LTD., NAKAGAI Masayuki). The
present inventors have determined the aggregation condition or
association condition of dyes by this small angle X-ray scattering
method. As a result, the aggregation condition or association
condition of dyes in an aqueous dye solution containing the first
coloring material and second coloring material has been found to be
as follows compared with an aqueous dye solution containing a
general cyan dye and the compound of the general formula (II) and
an aqueous dye solution containing only the general cyan dye.
Specifically, it has been found that in the aqueous dye solution
containing the first coloring material and second coloring
material, the aggregation condition or association condition of the
cyan coloring material is somewhat inhibited. It has also been
found that the aggregation condition of the dyes in the ink
according to the present invention is particularly inhibited in
aggregation. Accordingly, when used in combination with the
compound of the general formula (II), the aggregation of the
compound of the general formula (I) is more inhibited than the
general cyan dye. Therefore, it has been found that in the
permeation of the dye in an image formed into the ink-receiving
layer, the compound of the general formula (I) permeates deeper,
and the above-described effect is brought about.
<Adsorption Rate of Dye on Components Making Up Ink-receiving
Layer>
The adsorption rate of a general cyan dye on components making up
an ink-receiving layer when the cyan dye was used in combination
with the compound of the general formula (II) was almost the same
as an adsorption rate when this general cyan dye was singly used.
In any case, the adsorption rate was about 100%. However, in the
case of the compound of the general formula (I), the adsorption
rate thereof was found to be changed when used in combination with
the compound of the general formula (II). Specifically, the
adsorption rate when the compound of the general formula (I) was
singly used was about 100%, while the adsorption rate of the
compound of the general formula (I) when the compound of the
general formula (I) was used in combination with the compound of
the general formula (II) was lowered to about 40%.
Incidentally, the term "adsorption rate" in the present invention
means a proportion of a coloring material adsorbed on a material
(for example, aluminum oxide) forming an ink-receiving layer of a
recording medium. This adsorption rate can be calculated out by
adding an aqueous solution containing a dye the absorbance of which
has been measured in advance to an aqueous solution containing, for
example, an alumina dispersion, stirring the resultant mixed
solution for a certain period of time and then measuring the
absorbance of the aqueous solution.
As a result of the investigation by the present inventors, such a
phenomenon in the compound of the general formula (I) as described
above has been found to show the same tendency in not only the case
where the component forming the ink-receiving layer is an alumina
system, but also the case where the component forming the
ink-receiving layer is another general material such as a silica
system. From the result of the above-described investigation, it
can be understood that the ink according to the present invention
can markedly inhibit the lowering of ozone fastness of the
resulting image.
In order to confirm a predominant element for achieving the
above-described effect from the respective structures of the first
coloring material and second coloring material, the present
inventors have carried out an investigation by separating
respective elements to establish the technology of the present
invention. First, description is given with reference to FIGS. 7A
to 7E that are typical views illustrating existing positions of
respective coloring materials in an ink-receiving layer of a
recording medium in the case where inks respectively containing the
respective coloring materials have been separately applied to the
recording medium.
When an ink containing only a general cyan dye O1002 as a coloring
material was applied to a recording medium, the dye O1002 existed
at a shallow position (in the vicinity of the surface) in the
thickness-wise direction of an ink-receiving layer O1001 of the
recording medium as illustrated in FIG. 7A. When an ink containing
only the compound O1003 of the general formula (I) was applied to a
recording medium, the compound O1003 of the general formula (I)
existed at a shallow position (in the vicinity of the surface) in
the thickness-wise direction of an ink-receiving layer O1001 of the
recording medium like the above as illustrated in FIG. 7B.
When an ink containing the general cyan dye O1002 and another
general dye O1004 was applied to a recording medium, these dyes
also existed at a shallow position (in the vicinity of the surface)
in the thickness-wise direction of an ink-receiving layer O1001 of
the recording medium as illustrated in FIG. 7C. When an ink
containing the general cyan dye O1002 and the compound O1005 of the
general formula (II) was applied to a recording medium, these dyes
also existed at a shallow position (in the vicinity of the surface)
in the thickness-wise direction of an ink-receiving layer O1001 of
the recording medium as illustrated in FIG. 7D. The shallow
position in the thickness-wise direction of the ink-receiving layer
O1001 of the recording medium will hereinafter be referred to as
"vicinity of the surface of the ink-receiving layer".
When oxide gases such as ozone gas in the air cause such a reaction
that a coloring material is deteriorated when the coloring material
exists in such a state as described above in the ink-receiving
layer of the recording medium, the degree of deterioration of a
cyan component existing in the vicinity of the surface of the
ink-receiving layer becomes great. The compound of the general
formula (I) that is a cyan dye used in the present invention also
exists in the vicinity of the surface of the ink-receiving layer
when the resulting ink contains only the compound as a coloring
material because the adsorption rate of the compound on the
component making up the ink-receiving layer of the recording medium
is high.
However, as illustrated in FIG. 7E, in an ink containing the
compound O1003 of the general formula (I) and the compound O1005 of
the general formula (II) as coloring materials, the existing
positions of the respective coloring materials in the ink-receiving
layer of the recording medium are as follows. Namely, these
coloring materials are used in combination, whereby the adsorption
rate of the compound O1003 of the general formula (I) on the
ink-receiving layer O1001 becomes relatively low as described
above. Therefore, the compound O1003 of the general formula (I)
comes to exist at a position somewhat permeated in the
thickness-wise direction of the ink-receiving layer O1001 compared
with the case of FIG. 7B. As a result, it is inferred that the
contact of the compound of the general formula (I) with oxide gases
such as ozone gas in air is relieved when the coloring materials
are used in combination as described above, and so the
deterioration of a cyan component is inhibited, and the ozone
fastness of the resulting image is improved.
Incidentally, in the case of the general cyan dye O1002, the
adsorption rate on the component making up the ink-receiving layer
O1001 remains high even when the cyan dye is used in combination
with the compound O1005 of the general formula (II). Therefore, a
marked difference is not found in the existing position of the
coloring material as illustrated in FIG. 7D.
The present inventors infer that the reason why the existing
position of the compound of the general formula (I) in the
ink-receiving layer of the recording medium when the ink containing
the compound of the general formula (I) and the compound of the
general formula (II) in combination is used shows such specific
behavior as described above is as follows.
A software (WinMOPAC 3.9Pro; manufactured by FUJITSU) capable of
calculating molecular orbits was used to find a stabilized
structure of the compound of the general formula (II), and the
following fact was found. Specifically, in the compound of the
general formula (II), nitrogen atoms on the pyrazole rings having
no amino group face each other and exist as a circular structure.
The compound of the general formula (II) interacts with a triazine
ring of the compound of the general formula (I), thereby taking
such a state that the compound of the general formula (I) overlaps
with the compound of the general formula (II). The interaction to
the compound of the general formula (II) of the compound of the
general formula (I) taking such a state is greater than the
adsorption force thereof on the component making up the
ink-receiving layer. On the other hand, the compound of the general
formula (I) shows a decreased adsorption rate on the ink-receiving
layer and comes to exist together with the compound of the general
formula (II) at a position somewhat permeated in the thickness-wise
direction of the ink-receiving layer. In such a manner, an image
formed with the ink containing the compound of the general formula
(I) and the compound of the general formula (II) is considered to
be particularly markedly suppress deterioration caused by
ozone.
As a result of an investigation by the present inventors, it has
been found that the following phenomenon is caused by using, in
combination, a phthalocyanine coloring material whose substituent
contains a triazine ring and a compound having a skeleton in which
(a plurality of) nitrogen-containing aromatic heterocyclic rings
are directly bonded to a triazine ring. Specifically, it has been
found that the above compound lowers the adsorption rate of the
phthalocyanine coloring material on the ink-receiving layer,
thereby improving the ozone fastness of the resulting image. A
compound having a partial element structure of the compound
represented by the general formula (I), which is the first coloring
material, may hereinafter be referred to as "phthalocyanine
coloring material". A compound having a partial element structure
of the compound represented by the general formula (II), which is
the second coloring material, may be referred to as "compound
having a skeleton in which (a plurality of) nitrogen-containing
aromatic heterocyclic rings are directly bonded to a triazine
ring".
The present inventors have calculated molecular orbits for
analyzing the factors thereof. As a result, it has been found that
the following phenomenon is caused. Specifically, the triazine ring
in the phthalocyanine coloring material approaches
nitrogen-containing aromatic heterocyclic rings of the triazine
ring in the other compound, whereby an existing interval (distance)
between molecules of the phthalocyanine coloring material is
widened. As a result, it has been found that the association
condition of the phthalocyanine coloring material is hard to be
taken. As a result, it is considered that the interaction between
the phthalocyanine coloring material and the compound becomes
strong, and the adsorption rate of the phthalocyanine coloring
material on the ink-receiving layer is lowered. It has further been
found that the phthalocyanine coloring material has
nitrogen-containing aromatic heterocyclic ring(s) in its
phthalocyanine skeleton, thereby the synergistic effect thereof is
more increased. It has also been found that when the
nitrogen-containing aromatic heterocyclic ring is a pyridine ring
or pyrazine ring in particular, the synergistic effect is markedly
increased. In this case, the nitrogen-containing aromatic
heterocyclic ring in this compound particularly favorably has an
amino group because the solubility of such a compound comes not to
depend on pH, and the synergistic effect with the phthalocyanine
coloring material can be retained more stably. When the compound is
a compound having such a skeleton that a plurality of
nitrogen-containing aromatic heterocyclic rings are directly bonded
to the triazine ring, an existing interval (distance) between
molecules of the phthalocyanine dye can be more widened. Therefore,
the range of distribution of the phthalocyanine dye in the
thickness-wise direction of the recording medium can be more
widened, and so such a compound is particularly favorable. The
nitrogen-containing aromatic heterocyclic ring in the above
compound particularly favorably has an amino group because the
solubility of this compound comes not to depend on pH as described
above. In the present invention, the effect is the greatest so far
as the above compound is a compound of the general formula (II),
which satisfies all these conditions at the same time.
From the above, an ink having the following respective
constitutions is provided, whereby an ink markedly exhibiting the
above effects of the present invention can be obtained. (1) An ink
containing a phthalocyanine coloring material which has a pyridine
ring or pyrazine ring in the phthalocyanine skeleton thereof and
has a substituent containing a triazine ring, and a compound having
a skeleton in which a triazine ring is directly bonded to a
nitrogen-containing aromatic heterocyclic ring; (2) an ink
containing a phthalocyanine coloring material which has a
nitrogen-containing aromatic heterocyclic ring in the
phthalocyanine skeleton thereof and has a substituent containing a
triazine ring, and a compound having a skeleton in which a triazine
ring is directly bonded to the nitrogen-containing aromatic
heterocyclic ring; (3) an ink containing a phthalocyanine coloring
material which has a nitrogen-containing aromatic heterocyclic ring
in the phthalocyanine skeleton thereof and has a substituent
containing the triazine ring, and a compound having a skeleton in
which a triazine ring is directly bonded to a plurality of
nitrogen-containing aromatic heterocyclic rings; and (4) an ink
containing a phthalocyanine coloring material which has a
nitrogen-containing aromatic heterocyclic ring in the
phthalocyanine skeleton thereof and has a substituent containing a
triazine ring, and a compound represented by the general formula
(II). In each of the inks having the respective constitutions (1),
(2), (3) and (4), the nitrogen-containing aromatic heterocyclic
ring in the compound favorably has an amino group.
[Third Coloring Material: Compound Represented by the General
Formula (III), Compound Represented by the General Formula (IV)
and/or Compound Represented by the General Formula (V)]
The ink according to the present invention favorably further
contains a third coloring material in addition to the first
coloring material and the second coloring material. As the third
coloring material, is used at least one compound selected from the
group consisting of a compound represented by the following general
formula (III), a compound represented by the following general
formula (IV) and a compound represented by the following general
formula (V). Incidentally, at least one compound selected from the
group consisting of the compound represented by the following
general formula (III), the compound represented by the following
general formula (IV) and the compound represented by the following
general formula (V) is referred to as the third coloring material
in the following description. A gray ink providing an image
excellent in ozone fastness and color tone can be obtained by
using, in combination, the third coloring material in addition to
the above-described first coloring material and second coloring
material.
##STR00023## wherein R's are, independently of each other, a
hydrogen atom, alkyl group, hydroxyl group, cyclohexyl group
monoalkylaminoalkyl group or dialkylaminoalkyl group, M's are,
independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium, and X is a linking group;
The R's in the general formula (III) are, independently of each
other, a hydrogen atom, alkyl group, hydroxyl group, cyclohexyl
group monoalkylaminoalkyl group or dialkylaminoalkyl group.
Examples of the alkyl group include alkyl groups having 1 to 8
carbon atoms. Specific examples thereof include methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl,
n-pentyl, n-hexyl, n-heptyl and n-octyl.
Examples of the hydroxyalkyl group include hydroxyalkyl groups
having 1 to 4 carbon atoms. Specific examples thereof include
hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl. The
alkyl in the hydroxyalkyl may be a linear, branched or cyclic
alkyl, and a linear alkyl is particularly favorable. The
substitution position of the hydroxy in the hydroxyalkyl may be any
position. However, for example, a 2-hydroxyethyl, 3-hydroxypropyl
or 4-hydroxybutyl with the hydroxy substituted at its terminal is
particularly favorable.
Examples of the monoalkylaminoalkyl group include
mono-(C1-C4)alkylamino-(C1-C4)alkyl groups. Specific examples
thereof include monomethylaminopropyl and monoethylaminopropyl.
Examples of the dialkylaminoalkyl group include
di-(C1-C4)alkylamino-(C1-C4)alkyl groups. Specific examples thereof
include dimethylaminopropyl and diethylaminoethyl.
In the present invention, R in the general formula (III) is
favorably a hydrogen atom, alkyl group or cycloalkyl group, more
favorably a hydrogen atom or alkyl group, and particularly
favorably a methyl group.
X in the general formula (III) is a linking group. Examples of the
linking group include the following linking groups 1 to 7. In the
linking groups 1 to 7, a bond indicated with "*" is a bond of each
nitrogen atom and directly bonded to each of different two triazine
rings in the general formula (III). Among the following linking
groups, the linking group 1 is particularly favorably used.
##STR00024## wherein n is 2 to 8, favorably 2 to 6, more favorably
2, and `*`s are respective linking sites to different two triazine
rings.
##STR00025## wherein R.sub.a are, independently of each other, a
hydrogen atom or methyl group, and `*`s are respective linking
sites to different two triazine rings.
##STR00026## wherein `*`s are respective linking sites to different
two triazine rings.
##STR00027## wherein `*`s are respective linking sites to different
two triazine rings.
##STR00028## wherein `*`s are respective linking sites to different
two triazine rings.
##STR00029## wherein m is 2 to 4, and `*`s are respective linking
sites to different two triazine rings.
##STR00030## wherein `*`s are respective linking sites to different
two triazine rings.
M's in the general formula (III) are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium.
Examples of the alkali metal include lithium, sodium and potassium.
Examples of the organic ammonium include acetamido, benzamido,
methylamino, butylamino, diethylamino, phenylamino and
triethanolamino.
##STR00031## wherein R.sub.1 is a hydrogen atom or alkyl group, m
is an integer of 1 to 3, and M's are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium.
R.sub.1 in the general formula (IV) is a hydrogen atom or alkyl
group. The alkyl group favorably has 1 to 3 carbon atoms from the
viewpoint of solubility in an aqueous medium making up an ink, and
specific examples thereof include methyl, ethyl, primary propyl and
secondary propyl groups. Incidentally, if the number of carbon
atoms in the alkyl group is 4 or more, the hydrophobicity of such a
coloring material becomes high, and so the coloring material may
not be dissolved in the aqueous medium making up the ink.
M's in the general formula (IV) are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium.
Examples of the alkali metal include lithium, sodium and potassium.
Examples of the organic ammonium include acetamido, benzamido,
methylamino, butylamino, diethylamino, phenylamino and
triethanolamino.
##STR00032## wherein R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are,
independently of one another, an alkyl group, and M's are,
independently of one another, a hydrogen atom, alkali metal,
ammonium or organic ammonium.
R.sub.2, R.sub.3, R.sub.4 and R.sub.5 in the general formula (V)
are, independently of one another, an alkyl group. The alkyl group
favorably has 1 to 3 carbon atoms from the viewpoint of solubility
in an aqueous medium making up an ink, and specific examples
thereof include methyl, ethyl, primary propyl and secondary propyl
groups. Incidentally, if the number of carbon atoms in the alkyl
group is 4 or more, the hydrophobicity of such a coloring material
becomes high, and so the coloring material may not be dissolved in
the aqueous medium making up the ink.
M's in the general formula (V) are, independently of one another, a
hydrogen atom, alkali metal, ammonium or organic ammonium. Examples
of the alkali metal include lithium, sodium and potassium. Examples
of the organic ammonium include acetamido, benzamido, methylamino,
butylamino, diethylamino, phenylamino and triethanolamino.
As specific favorable examples of the compound of the general
formula (III), the compound of the general formula (IV) and the
compound of the general formula (V), may be mentioned the following
Exemplified Compounds III-1, III-2, IV-1, IV-2, and V-1 to V-3.
Incidentally, the following Exemplified Compounds are described in
the form of a free acid. Needless to say, the compounds of the
general formula (III), the general formula (IV) and the general
formula (V) in the present invention are not limited to the
following Exemplified Compounds so far as the compounds are
embraced in the structures of the general formula (III), the
general formula (IV) and the general formula (V) and definitions
thereof. Among the following Exemplified Compounds, Exemplified
Compound III-1, Exemplified Compound IV-1 or Exemplified Compound
V-2 is favorably used in the present invention, and Exemplified
Compound V-2 is particularly favorably used.
##STR00033## ##STR00034##
[Content of Third Coloring Material]
The ink according to the present invention favorably contains, as
the third coloring material, at least one compound selected from
the group consisting of such respective compounds of the general
formula (III), the general formula (IV) and the general formula (V)
as described above. In this case, the content (% by mass) of the
third coloring material in the ink is favorably from 0.1% by mass
or more to 10.0% by mass or less based on the total mass of the
ink.
The total of the content (% by mass) of the first coloring
material, the content (% by mass) of the second coloring material
and the content (% by mass) of the third coloring material in the
ink is favorably from 1.0% by mass or more to 10.0% by mass or less
based on the total mass of the ink. The total of the content (% by
mass) of these coloring materials is particularly favorably from
1.5% by mass or more to 7.0% by mass or less. If the total content
is less than 1.0% by mass, the ozone fastness and color
developability of the resulting image with such an ink may not be
sufficiently achieved in some cases. If the total content of the
coloring materials exceeds 10.0% by mass, the ink jet properties
such as sticking resistance may not be achieved in some cases.
The content (% by mass) of the third coloring material based on the
total mass of the ink is favorably from 0.5 times or more to 5.0
times or less in terms of mass ratio to the total of the content (%
by mass) of the first coloring material and the content (% by mass)
of the second coloring material (total of first coloring material
and second coloring material/third coloring material). The mass
ratio is particularly favorably from 1.0 time or more to 3.0 times
or less. The mass ratio of the contents is controlled within the
above range, whereby the resulting ink can provide an image
excellent in ozone fastness and light fastness and moreover can
achieve a color tone favorable for gray ink.
Incidentally, when the first coloring material, the second coloring
material and the third coloring material are used in combination, a
favorable range of a mass ratio of the first coloring material to
the second coloring material (first coloring material/second
coloring material) based on the total mass of the ink is as
described above.
[Color Tone Favorable for Gray Ink]
The color tone favorable for a gray ink, i.e., the color tone that
is neutral and provides a favorable image, in the present invention
specifically means the following. With respect to an image having
gradation property formed with a gray ink by gradually lowering a
recording duty from 100%, a* and b* in the L*a*b* color space
prescribed by CIE (International Commission on Illumination) are
measured. When the values of a* and b* in at least a portion where
the recording duty is 100% are -5.ltoreq.a*.ltoreq.10 and
-10.ltoreq.b*.ltoreq.1, respectively, such an ink is defined as an
ink having a color tone favorable for gray ink in the present
invention. An ink satisfying the following provisions is defined as
an ink having a color tone more favorable for gray ink. Namely, it
is favorable that the values of a* and b* in the portion where the
recording duty is 100% are -0.5.ltoreq.a*.ltoreq.5 and
-6.5.ltoreq.b*.ltoreq.0, respectively. Incidentally, the values of
a* and b* can be measured by means of, for example, a
spectrophotometer (trade name: Spectrolino; manufactured by Gretag
Macbeth). Needless to say, the present invention is not limited
thereto.
In the present invention, a gray ink is favorably prepared so as to
have the color tone favorable for gray ink within the above range
of the mass ratio among the first coloring material, second
coloring material and third coloring material. Incidentally, the
adjustment to the range of the color tone favorable for gray ink
can be conducted by suitably determining the contents of the
respective coloring materials within the above range of the mass
ratio. In order to achieve the color tone favorable for gray ink,
it is particularly favorable to use the compound of the general
formula (V) as the third coloring material.
[Fourth Coloring Material: Compound Represented by the General
Formula (VI) and/or Compound Represented by the General Formula
(VII)]
The ink according to the present invention may further contain, as
a fourth coloring material, at least one compound selected from a
compound represented by the following general formula (VI) and a
compound represented by the following general formula (VII) in
addition to the above-described coloring materials. Specifically,
an ink containing the fourth coloring material in addition to the
first coloring material and second coloring material, and an ink
containing the fourth coloring material in addition to the first
coloring material, second coloring material and third coloring
material are included. The ink containing the fourth coloring
material in addition to the first coloring material, second
coloring material and third coloring material is particularly
favorable.
##STR00035## wherein R.sub.10 are, independently of each other, a
hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group
having 1 to 4 carbon atoms, which may be substituted by a hydroxyl
group or an alkoxy group having 1 to 4 carbon atoms, an alkoxy
group having 1 to 4 carbon atoms, which may be substituted by a
hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, an
alkylamino group having 1 to 4 carbon atoms, which may be
substituted by a hydroxyl group or an alkoxy group having 1 to 4
carbon atoms, a carboxy-(C1-C5)alkylamino group, a
bis[carboxy-(C1-C5)alkyl]amino group, an alkanoylamino group having
1 to 4 carbon atoms, which may be substituted by a hydroxyl group
or an alkoxy group having 1 to 4 carbon atoms, a phenylamino group,
which may be substituted by a carboxyl, sulfonic or amino group, a
sulfonic group, a halogen atom, or a ureido group, [C] is an
aliphatic amine residue having a carboxyl or sulfonic group, and
M's are, independently of one another, a hydrogen atom, alkali
metal, ammonium or organic ammonium.
R.sub.10 in the general formula (VI) are, independently of each
other, a hydrogen atom, a hydroxyl group, a carboxyl group, an
alkyl group having 1 to 4 carbon atoms, which may be substituted by
a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, an
alkoxy group having 1 to 4 carbon atoms, which may be substituted
by a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms,
an alkylamino group having 1 to 4 carbon atoms, which may be
substituted by a hydroxyl group or an alkoxy group having 1 to 4
carbon atoms, a carboxy-(C1-C5)alkylamino group, a
bis[carboxy-(C1-C5)alkyl]amino group, an alkanoylamino group having
1 to 4 carbon atoms, which may be substituted by a hydroxyl group
or an alkoxy group having 1 to 4 carbon atoms, a phenylamino group,
which may be substituted by a carboxyl, sulfonic or amino group, a
sulfonic group, a halogen atom, or a ureido group.
Specific examples of the alkyl group having 1 to 4 carbon atoms,
which may be substituted by a hydroxyl group or an alkoxy group
having 1 to 4 carbon atoms, include the following groups: methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, methoxyethyl, ethoxyethyl, n-propoxyethyl,
isopropoxyethyl, n-butoxyethyl, sec-butoxyethyl, tert-butoxyethyl
and 2-hydroxyethyl.
Specific examples of the alkoxy group having 1 to 4 carbon atoms,
which may be substituted by a hydroxyl group or an alkoxy group
having 1 to 4 carbon atoms, include the following groups: methoxy,
ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy,
2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxy-propoxy,
methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy,
n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy,
isopropoxybutoxy, n-propoxybutoxy and 2-hydroxyethoxyethoxy.
Specific examples of the alkylamino group having 1 to 4 carbon
atoms, which may be substituted by a hydroxyl group or an alkoxy
group having 1 to 4 carbon atoms, include the following groups:
methylamino, ethylamino, n-propylamino, isopropyl-amino,
n-butyl-amino, isobutylamino, N,N-dimethylamino, N,N-diethyl-amino,
N,N-di(n-propyl)amino, N,N-di(isopropyl)amino, hydroxyethylamino,
2-hydroxypropylamino, 3-hydroxy-propylamino,
bis(hydroxyethyl)amino, methoxyethylamino, ethoxyethylamino,
bis(methoxyethyl)amino and bis(2-ethoxyethyl)amino.
Specific examples of the carboxy-(C1-C5)alkylamino group include
carboxymethylamino, carboxyethylamino, carboxypropylamino,
carboxy-n-butylamino and carboxy-n-pentylamino.
Specific examples of the bis[carboxy-(C1-C5)-alkyl]amino group
include bis(carboxymethyl)amino, bis(carboxyethyl)amino and
bis(carboxypropyl)amino.
Specific examples of the alkanoylamino group having 1 to 4 carbon
atoms, which may be substituted by a hydroxyl group or an alkoxy
group having 1 to 4 carbon atoms, include the following groups:
acetylamino, n-propionylamino, isopropionylamino,
hydroxyacetylamino, 2-hydroxy-n-propionylamino,
3-hydroxy-n-propionylamino, 2-methoxy-n-propionylamino,
3-methoxy-n-propionylamino, 2-hydroxy-n-butyrylamino,
3-hydroxy-n-butyrylamino, 2-methoxy-n-butyrylamino and
3-methoxy-n-butyrylamino.
Specific examples of the phenylamino group, which may be
substituted by a carboxyl, sulfonic or amino group, include the
following groups: phenylamino, sulfophenylamino,
carboxyphenylamino, biscarboxy-phenylamino, aminophenylamino,
diaminophenylamino and diaminosulfophenylamino.
Specific examples of the halogen atom include chlorine, bromine and
iodine atoms. Among these, the chlorine or bromine atom is
favorable, and the chlorine atom is particularly favorable.
Specific examples of the ureido group include 3-methylureido,
3,3-dimethylureido and 3-phenylureido groups.
[C] in the general formula (VI) is an aliphatic amine residue
having a carboxyl or sulfonic group. The aliphatic amine residue is
favorably a mono(C1-C5)alkylamine residue or di(C1-C5)alkylamine
residue having a carboxyl or sulfonic group. Specific examples of
the aliphatic amine residue having a carboxyl or sulfonic group
include the following groups: amino-(C1-C5)alkylsulfonic acid,
diimino-(C1-C5)alkylsulfonic acid, amino-(C1-C5)alkylcarboxylic
acid and diimino-(C1-C5)alkylcarboxylic acid. Among these, the
amine residues whose aliphatic group has 1 or 2 carbon atoms are
favorable. Sulfoethylamino and dicarboxymethylimino groups are
particularly favorable as the aliphatic amine residue, and the
sulfoethylamino group is further favorable.
M's in the general formula (VI) are, independently of one another,
a hydrogen atom, alkali metal, ammonium or organic ammonium.
Specific examples of the alkali metal include lithium, sodium and
potassium. Specific examples of the organic ammonium include
acetamido, benzamido, methylamino, butylamino, diethylamino and
phenylamino.
The compound of the general formula (VI) used in the present
invention is favorably such that R.sub.10 is an alkyl having 1 to 4
carbon atoms, and more favorably such that R.sub.10 is a methyl
group.
The compound of the general formula (VI) used in the present
invention favorably has a maximum absorption wavelength
(.lamda..sub.max) of 400 nm or more and 440 nm or less in an
absorption spectrum measured by using water as a solvent.
Specific favorable examples of the compound of the general formula
(VI) include the following Exemplified Compounds VI-1 to VI-12.
Exemplified Compounds VI-1 to VI-12 are compounds of the following
general formula (VIII) of which [C] is the aliphatic amine residues
shown in the following Table 2. Incidentally, the compounds of the
general formula (VI) in the present invention are not limited to
the following Exemplified Compounds so far as the compounds are
embraced in the structure of the general formula (VI). Among the
following Exemplified Compounds, Exemplified Compounds VI-1, VI-5
and VI-9 are particularly favorably used in the present
invention.
##STR00036## wherein M's are, independently of one another, a
hydrogen atom, alkali metal, ammonium or organic ammonium.
TABLE-US-00002 TABLE 2 Exemplified Compounds of general formula
(VI) Exemplified Compound [C] in general formula (VIII) VI-1
NH(CH.sub.2).sub.2SO.sub.3M VI-2 NH((CH.sub.2).sub.2COOM).sub.2
VI-3 NH(CH.sub.2).sub.2COOM VI-4 NH(CH.sub.2).sub.5COOM VI-5
NHCH.sub.2SO.sub.3M VI-6 N(CH.sub.2SO.sub.3M).sub.2 VI-7
N((CH.sub.2).sub.2SO.sub.3M).sub.2 VI-8 NHCH.sub.2COOM VI-9
N(CH.sub.2COOM).sub.2 VI-10 N((CH.sub.2).sub.3COOM).sub.2 VI-11
NH(CH.sub.2).sub.3SO.sub.3M VI-12
N((CH.sub.2).sub.3SO.sub.3M).sub.2
The compound of the following general formula (VII) used as the
fourth coloring material in the ink according to the present
invention will be now described in detail.
##STR00037## wherein A is an aromatic or heterocyclic group which
may be substituted, B is any group of the following general
formulae (1) to (5), and M's are, independently of each other, a
hydrogen atom, alkali metal, ammonium or organic ammonium.
##STR00038## wherein R.sub.1 to R.sub.9 are, independently of one
another, a hydrogen atom, halogen atom, aliphatic group, aromatic
group, heterocyclic group, carboxyl group, carbamoyl group,
alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic
oxycarbonyl group, acyl group, hydroxyl group, alkoxy group,
aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy
group, carbamoyloxy group, alkoxycarbonyloxy group,
aryloxycarbonyloxy group, amino group, acylamino group, ureido
group, sulfamoylamino group, alkoxycarbonylamino group,
aryloxycarbonylamino group, alkyl- or arylsulfonylamino group,
heterocyclic sulfonylamino group, cyano group, nitro group, alkyl-
or arylthio group, heterocyclic thio group, alkyl- or arylsulfonyl
group, heterocyclic sulfonyl group, alkyl- or arylsulfinyl group,
heterocyclic sulfinyl group, sulfamoyl group, or sulfonic group
with the proviso that each group may be further substituted.
A in the general formula (VII) is an aromatic or heterocyclic group
which may be substituted. Specific examples thereof include
substituents such as benzene ring, naphthalene ring, pyridine ring,
imidazole ring, pyrazole ring, thiazole ring, isothiazole ring,
thiadiazole ring, benzothiazole ring and benzoisothiazole ring.
Among these substituents, benzene ring, naphthalene ring, pyridine
ring, pyrazole ring, imidazole ring, isothiazole ring and
benzothiazole ring are favorable, and benzene ring and naphthalene
ring are more favorable.
B in the general formula (VII) is any group of the above-described
general formulae (1) to (5). R.sub.1 to R.sub.9 in the general
formulae (1) to (5) are, independently of one another, a hydrogen
atom, halogen atom, aliphatic group, aromatic group, heterocyclic
group, carboxyl group, carbamoyl group, alkoxycarbonyl group,
aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group,
hydroxyl group, alkoxy group, aryloxy group, heterocyclic oxy
group, silyloxy group, acyloxy group, carbamoyloxy group,
alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group,
acylamino group, ureido group, sulfamoylamino group,
alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl- or
arylsulfonylamino group, heterocyclic sulfonylamino group, cyano
group, nitro group, alkyl- or arylthio group, heterocyclic thio
group, alkyl- or arylsulfonyl group, heterocyclic sulfonyl group,
alkyl- or arylsulfinyl group, heterocyclic sulfinyl group,
sulfamoyl group, or sulfonic group with the proviso that each group
may be further substituted.
Examples of the halogen atom include chlorine, bromine and iodine
atoms. Among these halogen atoms, the chlorine and bromine atoms
are favorable, and the chlorine atom is more favorable.
Examples of the aliphatic group include alkyl, substituted alkyl,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aralkyl
and substituted aralkyl groups. These aliphatic groups may have a
branch or may form a cycle. The aliphatic group favorably has 1 to
20 carbon atoms, more favorably 1 to 16 carbon atoms. The aryl
portion of the aralkyl or substituted aralkyl group is favorably
phenyl or naphthyl, more favorably phenyl. Specific examples of the
aliphatic group include the following groups: methyl, ethyl, butyl,
isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl,
trifluoromethyl, 3-sulfo-propyl, 4-sulfobutyl, cyclohexyl, benzyl,
2-phenethyl, vinyl and allyl.
Examples of the aromatic group include monovalent or divalent aryl
groups and substituted aryl groups. The monovalent aromatic groups
include aryl groups and substituted aryl groups. The aryl group is
favorably phenyl or naphthyl, more favorably phenyl. The monovalent
aromatic group favorably has 6 to 20 carbon atoms, more favorably 6
to 16 carbon atoms. Specific examples of the monovalent aromatic
groups include phenyl, p-phenylphenyl, p-tolyl, p-methoxy-phenyl,
o-chlorophenyl, p-chlorophenyl, p-acetylamino-phenyl and
m-(3-sulfopropylamino)phenyl. Examples of the divalent aromatic
groups include those obtained by converting these monovalent
aromatic groups into divalent groups, and specific examples thereof
include phenylene, p-tolylene, p-methoxyphenylene,
o-chloro-phenylene, m-(3-sulfopropylamino)phenylene and
naphthylene.
Examples of the heterocyclic group include substituted heterocyclic
groups and unsubstituted heterocyclic groups. An alicyclic ring,
aromatic ring or another heterocyclic ring may be condensed with
the heterocyclic ring. The heterocyclic ring is favorably a
five-membered or six-membered heterocyclic ring. Examples of a
heteroatom of the heterocyclic ring include nitrogen, oxygen and
sulfur atoms. Specific examples of the substituent include
aliphatic groups, halogen atoms, alkyl- or arylsulfonyl groups,
acyl group, acylamino group, sulfamoyl group, carbamoyl group and
ionic hydrophilic groups. Examples of a monovalent heterocyclic
group include 2-pyridyl, 3-pyridyl, 2-thienyl, 2-thiazolyl,
2-benzothiazolyl, 2-benzoxazolyl and 2-furyl. Examples of a
divalent heterocyclic group include groups (i.e., bonds) obtained
by removing a hydrogen atom from the monovalent heterocyclic
groups.
Examples of the carbamoyl group include substituted and
unsubstituted carbamoyl groups. Specific examples of the
substituent include alkyl groups. Specific examples of the
carbamoyl group include methylcarbamoyl and dimethylcarbamoyl
groups.
Examples of the alkoxycarbonyl group include substituted and
unsubstituted alkoxycarbonyl groups. The alkoxycarbonyl group is
favorably an alkoxycarbonyl group having 2 to 20 carbon atoms.
Specific examples of the substituent include ionic hydrophilic
groups. Specific examples of the alkoxycarbonyl group include
methoxycarbonyl and ethoxycarbonyl groups.
Examples of the aryloxycarbonyl group include substituted and
unsubstituted aryloxycarbonyl groups. The aryloxycarbonyl group is
favorably an aryloxycarbonyl group having 7 to 20 carbon atoms.
Specific examples of the substituent include ionic hydrophilic
groups. Specific examples of the aryloxycarbonyl group include a
phenoxycarbonyl group.
Examples of the heterocyclic oxycarbonyl group include substituted
and unsubstituted heterocyclic oxycarbonyl groups. The heterocyclic
oxycarbonyl group is favorably a heterocyclic oxycarbonyl group
having 2 to 20 carbon atoms. Specific examples of the substituent
include ionic hydrophilic groups. Specific examples of the
heterocyclic oxycarbonyl group include 2-pyridyl-oxycarbonyl
group.
Examples of the acyl group include substituted and unsubstituted
acyl groups. The acyl group is favorably an acyl group having 1 to
20 carbon atoms. Specific examples of the substituent include ionic
hydrophilic groups. Specific examples of the acyl group include
acetyl and benzoyl groups.
Examples of the alkoxy group include substituted and unsubstituted
alkoxy groups. The alkoxy group is favorably an alkoxy group having
1 to 20 carbon atoms. Specific examples of the substituent include
alkoxy, hydroxyl and ionic hydrophilic groups. Specific examples of
the alkoxy group include methoxy, ethoxy, isopropoxy,
methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy groups.
Examples of the aryloxy group include substituted and unsubstituted
aryloxy groups. The aryloxy group is favorably an aryloxy group
having 6 to 20 carbon atoms. Specific examples of the substituent
include alkoxy and ionic hydrophilic groups. Specific examples of
the aryloxy group include phenoxy, p-methoxyphenoxy and
o-methoxyphenoxy groups.
Examples of the heterocyclic oxy group include substituted and
unsubstituted heterocyclic oxy groups. The heterocyclic oxy group
is favorably a heterocyclic oxy group having 2 to 20 carbon atoms.
Specific examples of the substituent include alkyl, alkoxy and
ionic hydrophilic groups. Specific examples of the heterocyclic oxy
group include 3-pyridyloxy and 3-thienyloxy groups.
The silyloxy group is favorably a silyloxy group substituted by an
aliphatic group having 1 to 20 carbon atoms and/or an aromatic
group. Specific examples of the silyloxy group include
trimethylsilyloxy and diphenylmethylsilyloxy groups.
Examples of the acyloxy group include substituted and unsubstituted
acyloxy groups. The acyloxy group is favorably an acyloxy group
having 1 to 20 carbon atoms. Specific examples of the substituent
include ionic hydrophilic groups. Specific examples of the acyloxy
group include acetoxy and benzoyloxy groups.
Examples of the carbamoyloxy group include substituted and
unsubstituted carbamoyloxy groups. Specific examples of the
substituent include alkyl groups. Specific examples of the
carbamoyloxy group include an N-methylcarbamoyloxy group.
Examples of the alkoxycarbonyloxy group include substituted and
unsubstituted alkoxy carbonyloxy groups. The alkoxycarbonyloxy
group is favorably an alkoxycarbonyloxy group having 2 to 20 carbon
atoms. Specific examples of the alkoxycarbonyloxy group include
methoxycarbonyloxy and isopropoxycarbonyloxy groups.
Examples of the aryloxycarbonyloxy group include substituted and
unsubstituted aryloxy-carbonyloxy groups. The aryloxycarbonyloxy
group is favorably an aryloxycarbonyloxy group having 7 to 20
carbon atoms. Specific examples of the aryloxy-carbonyloxy group
include a phenoxycarbonyloxy group.
Examples of the amino group include amino groups substituted by an
alkyl, aryl or heterocyclic group, and the alkyl, aryl and
heterocyclic groups may be further substituted. The alkylamino
group is favorably an alkylamino group having 1 to 20 carbon atoms.
Specific examples of the substituent include ionic hydrophilic
groups. Specific examples of the alkylamino group include
methylamino and diethylamino groups. Examples of the arylamino
group include substituted and unsubstituted arylamino groups. The
arylamino group is favorably an arylamino group having 6 to 20
carbon atoms. Specific examples of the substituent include halogen
atoms and ionic hydrophilic groups. Specific examples of the
arylamino group include anilino and 2-chlorophenylamino groups.
Examples of the heterocyclic amino group include substituted and
unsubstituted heterocyclic amino groups. The heterocyclic amino
group is favorably a heterocyclic amino group having 2 to 20 carbon
atoms. Specific examples of the substituent include alkyl groups,
halogen atoms and ionic hydrophilic groups.
Examples of the acylamino group include substituted and
unsubstituted acylamino groups. The acylamino group is favorably an
acylamino group having 2 to 20 carbon atoms. Specific examples of
the substituent include ionic hydrophilic groups. Specific examples
of the acylamino group include acetylamino, propionylamino,
benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino
groups.
Examples of the ureido group include substituted and unsubstituted
ureido groups. The ureido group is favorably a ureido group having
1 to 20 carbon atoms. Specific examples of the substituent include
alkyl and aryl groups. Specific examples of the ureido group
include 3-methylureido, 3,3-dimethylureido and 3-phenylureido
groups.
Examples of the sulfamoylamino group include substituted and
unsubstituted sulfamoylamino groups. Specific examples of the
substituent include alkyl groups. Specific examples of the
sulfamoylamino group include an N,N-dipropylsulfamoylamino
group.
Examples of the alkoxycarbonylamino group include substituted and
unsubstituted alkoxycarbonyl-amino groups. The alkoxycarbonylamino
group is favorably an alkoxycarbonylamino group having 2 to 20
carbon atoms. Specific examples of the substituent include ionic
hydrophilic groups. Specific examples of the alkoxycarbonylamino
group include an ethoxycarbonylamino group.
Examples of the aryloxycarbonylamino group include substituted and
unsubstituted aryloxycarbonyl-amino groups. The
aryloxycarbonylamino group is favorably an aryloxycarbonylamino
group having 7 to 20 carbon atoms. Specific examples of the
substituent include ionic hydrophilic groups. Specific examples of
the aryloxycarbonylamino group include a phenoxycarbonylamino
group.
Examples of the alkyl- or arylsulfonylamino group include
substituted and unsubstituted alkyl- or arylsulfonylamino groups.
The sulfonylamino group is favorably a sulfonylamino group having 1
to 20 carbon atoms. Specific examples of the substituent include
ionic hydrophilic groups. Specific examples of the sulfonylamino
group include methylsulfonylamino, N-phenylmethylsulfonylamino,
phenylsulfonylamino and 3-carboxyphenylsulfonylamino groups.
Examples of the heterocyclic sulfonylamino group include
substituted and unsubstituted heterocyclic sulfonylamino groups.
The heterocyclic sulfonylamino group is favorably a heterocyclic
sulfonylamino group having 1 to 12 carbon atoms. Specific examples
of the substituent include ionic hydrophilic groups. Specific
examples of the heterocyclic sulfonylamino group include
2-thiophenesulfonylamino and 3-pyridinesulfonylamino groups.
Examples of the alkyl- or arylthio group include substituted and
unsubstituted alkyl- or arylthio groups. The alkyl- or arylthio
group favorably has 1 to 20 carbon atoms. Specific examples of the
substituent include ionic hydrophilic groups. Specific examples of
the alkyl- or arylthio group include methylthio and phenylthio
groups.
Examples of the heterocyclic thio group include substituted and
unsubstituted heterocyclic thio groups. The heterocyclic thio group
favorably has 1 to 20 carbon atoms. Specific examples of the
substituent include ionic hydrophilic groups. Specific examples of
the heterocyclic thio group include a 2-pyridylthio group.
Examples of the alkyl- or arylsulfonyl group include substituted
and unsubstituted alkyl- or arylsulfonyl groups. Specific examples
of the alkyl- or arylsulfonyl group include methylsulfonyl and
phenylsulfonyl groups.
Examples of the heterocyclic sulfonyl group include substituted and
unsubstituted heterocyclic sulfonyl groups. The heterocyclic
sulfonyl group favorably has 1 to 20 carbon atoms. Specific
examples of the substituent include ionic hydrophilic groups.
Specific examples of the heterocyclic sulfonyl group include
2-thiophenesulfonyl and 3-pyridinesulfonyl groups.
Examples of the alkyl- or arylsulfinyl group include substituted
and unsubstituted alkyl- or arylsulfinyl groups. Specific examples
of the alkyl- or arylsulfinyl group include methylsulfinyl and
phenylsulfinyl groups.
Examples of the heterocyclic sulfinyl group include substituted and
unsubstituted heterocyclic sulfinyl groups. The heterocyclic
sulfinyl group favorably has 1 to 20 carbon atoms. Specific
examples of the substituent include ionic hydrophilic groups.
Specific examples of the heterocyclic sulfinyl group include a
4-pyridinesulfinyl group.
Examples of the sulfamoyl group include substituted and
unsubstituted sulfamoyl groups. Specific examples of the
substituent include alkyl groups. Specific examples of the
sulfamoyl group include dimethylsulfamoyl and
di-(2-hydroxyethyl)-sulfamoyl groups.
M's in the general formula (VII) are, independently of each other,
a hydrogen atom, alkali metal, ammonium or organic ammonium.
Specific examples of the alkali metal include lithium, sodium and
potassium. Specific examples of the organic ammonium include
acetamido, benzamido, methylamino, butylamino, diethylamino,
phenylamino and triethanolamino.
The compound of the general formula (VII) used in the present
invention is favorably such that A is a naphthyl group, which may
be substituted, B is a group represented by the general formula
(2), and R.sub.3 in the general formula (2) is an aryl or pyridyl
group. Specific favorable examples of the aryl and pyridyl groups
include the following groups: phenyl, 2-methylphenyl,
3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl,
2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl,
2,6-dimethylphenyl, 3,5-dimethyl-phenyl, 2,4,6-trimethylphenyl,
2,3,4-trimethyl-phenyl, 2,3,5-trimethylphenyl,
2,3,6-trimethylphenyl, 2-chloro-phenyl, 3-chlorophenyl,
4-chlorophenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl,
2-pyridyl, 3-pyridyl, 4-pyridyl, 1-naphthyl and 2-naphthyl groups.
Among these groups, phenyl, 3-methylphenyl, 4-methylphenyl,
2-chlorophenyl, 3-chlorophenyl, 2-pyridyl, 4-pyridyl, 1-naphthyl
and 2-naphthyl groups are favorable.
The compound of the general formula (VII) used in the present
invention favorably has a maximum absorption wavelength
(.lamda..sub.max) of 590 nm or more and 620 nm or less in an
absorption spectrum measured by using water as a solvent.
Specific favorable examples of the compound of the general formula
(VII) include the following Exemplified Compounds VII-1 to VII-12.
Incidentally, the compounds of the general formula (VII) in the
present invention are not limited to the following Exemplified
Compounds so far as the compounds are embraced in the structure of
the general formula (VII). Among the following Exemplified
Compounds, Exemplified Compounds VII-3, VII-5, VII-6, VII-8, VII-9,
VII-10, VII-11 and VII-12 are favorably used in the present
invention, and Exemplified Compounds VII-3, VII-5 and VII-10 are
more favorably used.
##STR00039## ##STR00040## ##STR00041## ##STR00042##
[Content of Fourth Coloring Material]
The ink according to the present invention favorably contains, as
the fourth coloring material, at least one compound selected from
the compounds of the general formulae (VI) and (VII) as described
above. In this case, the content (% by mass) of the fourth coloring
material in the ink is favorably from 0.05% by mass or more to
10.0% by mass or less based on the total mass of the ink.
The total of the content (% by mass) of the first coloring material
and the content (% by mass) of the second coloring material, and
the content (% by mass) of the third coloring material and the
content (% by mass) of the fourth coloring material contained as
needed in the ink is favorably from 1.0% by mass or more to 10.0%
by mass or less based on the total mass of the ink. The total of
the content (% by mass) of these coloring materials is particularly
favorably from 1.5% by mass or more to 7.0% by mass or less. If the
total content of the coloring materials is less than 1.0% by mass,
the ozone fastness and color developability of the resulting image
with such an ink may not be sufficiently achieved in some cases. If
the total content of the coloring materials exceeds 10.0% by mass,
the ink jet properties such as sticking resistance may not be
achieved in some cases.
The content (% by mass) of the fourth coloring material based on
the total mass of the ink is favorably within a specific range to
the other coloring materials. For example, the content is favorably
from 1.0 times or more to 70.0 times or less in terms of mass ratio
to the total of the content (% by mass) of the first coloring
material, the content (% by mass) of the second coloring material
and the content (% by mass) of the third coloring material (total
of first coloring material, second coloring material and third
coloring material/fourth coloring material). In the present
invention, the mass ratio is particularly favorably from 5.0 times
or more to 45.0 times or less. The mass ratio of the contents is
controlled within the above range, whereby a color tone close to a
neutral color tone and favorable for gray ink can be achieved. The
mass ratio of the contents is controlled within the above range,
whereby the resulting ink can provide an image excellent in ozone
fastness and light fastness, and moreover can more effectively
achieve a color tone favorable for gray ink and improve the
metamerism.
Incidentally, when the first coloring material, second coloring
material, third coloring material and fourth coloring material are
used in combination, a favorable range of mass ratio among the
first coloring material, second coloring material and third
coloring material (total of first coloring material and second
coloring material/third coloring material) based on the total mass
of the ink is as described above. When the first coloring material,
second coloring material and third coloring material are used in
combination, a favorable range of the mass ratio of the first
coloring material to the second coloring material (first coloring
material/second coloring material) based on the total mass of the
ink is also as described above.
The color tone favorable for gray ink is as described above. In the
present invention, a gray ink is particularly favorably prepared so
as to have the color tone favorable for gray ink within the above
range of the mass ratio among the first coloring material, second
coloring material, third coloring material and fourth coloring
material. Incidentally, the adjustment to the range of the color
tone favorable for gray ink can be conducted by suitably
determining the contents of the respective coloring materials
within the above range of the mass ratio. In order to achieve the
color tone favorable for gray ink, it is particularly favorable to
use the compound of the general formula (VII) as the fourth
coloring material.
[Mechanism for Improving Metamerism of a Resulting Image by Further
Using, in Combination, Fourth Coloring Material in Addition to
First Coloring Material and Second Coloring Material, and Third
Coloring Material Added as Needed]
The present inventors infer that a mechanism for improving the
metamerism in the resulting image by further containing the fourth
coloring material in the ink containing the first coloring material
and second coloring material, and the third coloring material added
as needed as described above is as follows.
In order to improve the metamerism of an image, it is important
that the ink used has absorption over the whole visible ray region
(from 380 nm to 780 nm), and the absorption spectrum is flat. Since
the respective absorption spectra of the first coloring material,
second coloring material and third coloring material used in the
present invention are in a relatively sharp form, absorption
intensity in a wavelength region between maximum absorption
wavelengths of the coloring materials becomes small. As a result,
the absorption spectrum of an ink containing the first coloring
material, second coloring material and third coloring material
causes difference in absorption intensity, so that it is difficult
to have absorption over the whole visible ray region and make the
absorption spectrum flat.
The fourth coloring material used in the present invention has
absorption in a wavelength region between the maximum absorption
wavelengths of the first coloring material, second coloring
material and third coloring material. Therefore, when the ink
containing the first coloring material and second coloring
material, and the third coloring material added as needed further
contains the fourth coloring material, such an ink has absorption
in a wide region of the visible ray region, and the absorption
spectrum of the ink becomes flat. It is considered that the
metamerism of the image is improved by such mechanism.
[Mechanism for Improving Light Fastness of a Resulting Image by
Using Compound of the General Formula (VII) as Fourth Coloring
Material]
The ink containing the first coloring material and second coloring
material, and the third coloring material used as needed
particularly favorably further contains the compound of the general
formula (VII) as the fourth coloring material, because both
metamerism and light fastness of the resulting image can be
improved. The present inventors infer that a mechanism for
improving both metamerism and light fastness is as follows.
According to the investigation by the present inventors, not only
the metamerism of the image, but also the light fastness is
improved by the ink containing the first coloring material and
second coloring material, and the third coloring material used as
needed and the compound of the general formula (VII) as the fourth
coloring material. When a recorded article is irradiated with
light, a yellow component in the recorded article is generally
particularly markedly deteriorated. On the other hand, the compound
of the general formula (VII) has such a property that the color
tone thereof changes toward yellow when irradiated with light.
Accordingly, the mechanism for improving the light fastness of the
image by using the ink making combined use of the above-described
coloring materials is considered to be attributable to the fact
that the yellow component in the recorded article, which has been
deteriorated by irradiation of the light, is remedied by the change
of the color tone toward yellow of the compound of the general
formula (VII).
[Verification Method of Coloring Material]
In order to verify whether the coloring materials used in the
present invention are contained in a liquid (ink) or not, the
following verification methods (1) to (3) using high performance
liquid chromatography (HPLC) can be applied. (1) Retention time of
peak; (2) Maximum absorption wavelength on the peak of (1); (3) M/Z
(posi) and M/Z (nega) of mass spectrum on the peak of (1).
Analytic conditions of the high performance liquid chromatography
are as follows. First, a liquid (ink) diluted to about 1/1,000 with
pure water was prepared and used as a sample for measurement. With
respect to the sample, analysis by the high performance liquid
chromatography was conducted under the following conditions to
measure the retention time and maximum absorption wavelength of a
peak. Column: SunFire C.sub.18 (manufactured by Nihon Waters K.K.),
2.1 mm.times.150 mm, column temperature: 40.degree. C.; Flow rate:
0.2 mL/min; PDA: 200 nm to 700 nm; Mobile phase and gradient
conditions: see Table 3.
TABLE-US-00003 TABLE 3 Mobile phase and gradient conditions 0 to 31
to 5 min 5 to 24 min 24 to 31 min 45 min A: pure water 85% 85
.fwdarw. 45% 45 .fwdarw. 0% 0% B: methanol 10% 10 .fwdarw. 50% 50
.fwdarw. 95% 95% C: 0.2 mmol/L aqueous 5% 5% 5% 5% solution of
ammonium acetate
Analytic conditions of the mass spectrum are as follows. With
respect to the resultant peak, the mass spectrum is measured under
the following conditions to measure M/Z most strongly detected for
posi and nega, respectively. Ionization method ESI Capillary
voltage: 3.5 kV Desolvent gas: 300.degree. C. Ion source
temperature: 120.degree. C. Detector posi: 40 V, 200 to 1500
amu/0.9 sec nega: 40 V, 200 to 1500 amu/0.9 sec.
According to the method and conditions described above, the
measurement was conducted on Exemplified Compound II-5 as a
representative example of the second coloring material, Exemplified
Compounds III-1, IV-1 and V-2 as representative examples of the
third coloring material, and Exemplified Compounds VI-1 and VII-5
as representative examples of the fourth coloring material. As a
result, the values of the resultant retention time, maximum
absorption wavelength, M/Z (posi) and M/Z (nega) are shown in Table
4. When the measurement is conducted on an unknown ink under the
same method and conditions as described above, and the resultant
respective values correspond to the values shown in Table 4, the
ink can be determined to contain a compound corresponding to the
compound used in the present invention.
TABLE-US-00004 TABLE 4 Analyzed results Exemplified Retention time
Maximum absorption M/Z Compound [min] wavelength [nm] posi nega
Second II-5 31.0 to 32.0 440 to 460 937 to 940 935 to 938 coloring
material Third III-1 18.0 to 19.0 500 to 520 990 to 993 987 to 990
coloring IV-1 23.0 to 25.0 530 to 550 941 to 944 469 to 471
material V-2 34.0 to 35.0 545 to 565 1176 to 1179 1174 to 1177 35.0
to 36.0 545 to 565 1176 to 1179 1174 to 1177 Fourth VI-1 30.0 to
31.0 410 to 430 573 to 576 1150 to 1153 coloring VII-5 29.0 to 30.0
600 to 620 1091 to 1094 1090 to 1093 material
(Aqueous Medium)
An aqueous solvent that is water or a mixed solvent of water and a
water-soluble organic solvent may be used in the ink according to
the present invention. Deionized water (ion-exchanged water) is
favorably used as the water. The content (% by mass) of water in
the ink is favorably 10.0% by mass or more and 90.0% by mass or
less based on the total mass of the ink.
No particular limitation is imposed on the water-soluble organic
solvent so far as the solvent is soluble in water, and alcohols,
polyhydric alcohols, polyglycols, glycol ethers,
nitrogen-containing polar solvents and sulfur-containing polar
solvents may be used. The content (% by mass) of the water-soluble
organic solvent in the ink is favorably 5.0% by mass or more and
90.0% by mass or less, more favorably 10.0% by mass or more and
50.0% by mass or less based on the total mass of the ink. If the
content of the water-soluble organic solvent is less than the above
range, reliability such as ejection stability may not be achieved
in some cases when the resulting ink is used in an ink jet
recording apparatus. If the content of the water-soluble organic
solvent is more than the above range, the viscosity of the
resulting ink may increase in some cases to cause feeding failure
of the ink.
Specific examples of usable water-soluble organic solvents include
alkyl alcohols having 1 to 4 carbon atoms, such as methyl alcohol,
ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl
alcohol, sec-butyl alcohol and tert-butyl alcohol; amides such as
dimethylformamide and dimethylacetamide; ketones and ketone
alcohols such as acetone and diacetone alcohol; ethers such as
tetrahydrofuran and dioxane; polyalkylene glycols such as
polyethylene glycol and polypropylene glycol; glycols such as
ethylene glycol, propylene glycol, butylene glycol, diethylene
glycol, triethylene glycol, hexylene glycol and thiodiglycol;
alkylene glycols the alkylene group of which has 2 to 6 carbon
atoms, such as 1,5-pentanediol, 1,6-hexanediol,
2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol and
1,2,6-hexanetriol; bis(2-hydroxyethyl)sulfone; alkyl ether acetates
such as polyethylene glycol monomethyl ether acetate; alkyl ethers
of polyhydric alcohols, such as ethylene glycol monomethyl (or
ethyl) ether, diethylene glycol methyl (or ethyl) ether and
triethylene glycol monomethyl (or ethyl) ether;
N-methyl-2-pyrrolidone; 2-pyrrolidone; and
1,3-dimethyl-2-imidazolidinone. Needless to say, the present
invention is not limited to these solvents. One or more of these
water-soluble organic solvents may be used as needed.
(Other Additives)
The ink according to the present invention may contain
water-soluble organic compounds being solid at ordinary
temperature, such as polyhydric alcohols such as trimethylolpropane
and trimethylolethane, and urea derivatives such as ethyleneurea in
addition to the above-described components as needed. In addition,
the ink according to the present invention may contain various
additives such as surfactants, pH adjustors, rust preventives,
preservatives, mildew proofing agents, antioxidants, anti-reducing
agents, evaporation accelerators, chelating agents and
water-soluble polymers as needed.
(Other Inks)
In order to form a full-color image, the ink according to the
present invention may be used in combination with inks having
substantially same color tone as the ink according to the present
invention or inks having another color tone than the ink according
to the present invention. The ink according to the present
invention is favorably used in combination with at least one ink
selected from, for example, black, cyan, magenta, yellow, red,
green and blue inks. The so-called light color inks respectively
having substantially the same color tones as these inks may also be
further used in combination. Coloring materials used in these inks
or light color inks may be publicly known dyes or newly synthesized
coloring materials.
<Recording Medium>
As a recording medium used upon forming an image with the ink
according to the present invention, any recording medium may be
used so far as the ink can be applied thereto to conduct recording.
In the present invention, a recording medium for ink jet in which a
coloring material such as a dye or pigment is caused to be adsorbed
on fine particles forming a porous structure of an ink-receiving
layer is favorably used. In particular, a recording medium having
the so-called interstice-absorbed type ink-receiving layer in which
an ink is absorbed in interstices formed in an ink-receiving layer
on a base material is favorably used. The interstice-absorbed type
ink-receiving layer is formed by mainly using fine particles and
may contain a binder and other additives as needed.
Specific examples of usable fine particles include inorganic
pigments such as silica, clay, talc, calcium carbonate, kaolin,
aluminum oxides such as alumina and alumina hydrate, diatomaceous
earth, titanium oxide, hydrotalcite, and zinc oxide; and organic
pigments such as urea-formalin resins, ethylene resins and styrene
resins. One or more kinds of these fine particles may be used as
needed.
As the binder, may be used a water-soluble polymer or latex.
Specific examples of usable binders include polyvinyl alcohol,
starch and gelatin, and modified products thereof, gum arabic,
cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl
cellulose and hydroxypropionylmethyl cellulose, SBR latexes, NBR
latexes, methyl methacrylate-butadiene copolymer latexes,
functional-group-modified polymer latexes, vinyl copolymer latexes
such as ethylene-vinyl acetate copolymers, polyvinyl pyrrolidone,
maleic anhydride polymers or copolymers thereof, and acrylic ester
copolymers. One or more of these binders may be used as needed.
In addition, additives may be used as needed. Examples of usable
additives include dispersing agents, thickeners, pH adjusters,
lubricants, flowability modifiers, surfactants, antifoaming agents,
parting agents, fluorescent whitening agents, ultraviolet
absorbents, antioxidants and dye fixers.
When an image is formed with the ink according to the present
invention, a recording medium with an ink-receiving layer formed
mainly of fine particles having an average particle size of 1 .mu.m
or less is favorably used. Specific examples of the fine particles
include fine silica particles and fine aluminum oxide particles. As
the fine silica particles, fine silica particles typified by
colloidal silica are favorable. A commercially available product
may also be used as the colloidal silica. However, colloidal silica
described in, for example, Japanese Patent Nos. 2803134 and 2881847
is favorably used. As favorable examples of the fine aluminum oxide
particles, may be mentioned fine alumina hydrate particles (alumina
pigments).
Among the alumina pigments, alumina hydrates such as pseudoboehmite
represented by the following formula are particularly favorably
used. AlO.sub.3--n(OH).sub.2n.mH.sub.2O wherein n is an integer of
1 to 3, and m is a number of 0 to 10, favorably 0 to 5, with the
proviso that m and n are not 0 at the same time.
In many cases, mH.sub.2O represents an aqueous phase which does not
participate in the formation of a crystal lattice, but can be
eliminated. Therefore, m may take a value other than an integer.
When this kind of alumina hydrate is heated, m may reach a value of
0.
The alumina hydrate can be prepared according to such a publicly
known process as described below. For example, the alumina hydrate
can be prepared by hydrolysis of an aluminum alkoxide or sodium
aluminate as described in U.S. Pat. Nos. 4,242,271 and 4,202,870.
The alumina hydrate can also be prepared by a process in which an
aqueous solution of sodium sulfate or aluminum chloride is added to
an aqueous solution of sodium aluminate to conduct neutralization
as described in Japanese Patent Publication No. S57-044605.
The recording medium favorably has abase material for supporting
the ink-receiving layer. No particular limitation is imposed on the
base material so far as an ink-receiving layer can be formed on the
base material by the porous fine particles, and a stiffness
sufficient for conveyance by a conveying mechanism such as a ink
jet recording apparatus can be obtained, and any base material may
be used. For example, a paper base material formed of a pulp
material composed mainly of natural cellulose fibers may be used. A
plastic base material formed of a material such as polyester (for
example, polyethylene terephthalate), cellulose triacetate,
polycarbonate, polyvinyl chloride, polypropylene or polyimide may
also be used. Further, resin-coated paper (for example, RC paper)
having a polyolefin resin coated layer, to which a white pigment is
added, on at least one surface of a paper substrate may be
used.
<Ink Jet Recording Method>
The ink according to the present invention is used in an ink jet
recording method performed in the present invention, in which an
ink is ejected by an ink jet system to conduct recording on a
recording medium. Examples of the ink jet recording method include
a recording method in which mechanical energy is applied to an ink
to eject the ink, and a recording method in which thermal energy is
applied to an ink to eject the ink. In particular, the ink jet
recording method utilizing thermal energy may be favorably used in
the present invention.
<Ink Cartridge>
An ink cartridge suitable for conducting recording with the ink
according to the present invention includes an ink cartridge
according to the present invention equipped with an ink storage
portion storing such an ink.
<Recording Unit>
A recording unit suitable for conducting recording with the ink
according to the present invention includes a recording unit
according to the present invention equipped with an ink storage
portion storing such an ink and a recording head for ejecting the
ink. In particular, a recording unit of which the recording head
ejects an ink by applying thermal energy corresponding to a
recording signal to the ink may favorably be used. In particular, a
recording head having a liquid-contacting face of a heat-generating
portion containing a metal and/or a metal oxide is favorably used.
Specific examples of the metal and/or the metal oxide making up the
liquid-contacting face of the heat-generating portion include
metals such as Ta, Zr, Ti, Ni and Al, and oxides of these
metals.
<Ink Jet Recording Apparatus>
An ink jet recording apparatus suitable for conducting recording
with the ink according to the present invention includes an ink jet
recording apparatus according to the present invention equipped
with an ink storage portion storing such an ink and a recording
head for ejecting the ink. In particular, an ink jet recording
apparatus with which an ink is ejected by applying thermal energy
corresponding to a recording signal to the ink in the interior of
the recording head having the ink storage portion storing the ink
is mentioned.
The schematic construction of a mechanism portion of the ink jet
recording apparatus will hereinafter be described. The ink jet
recording apparatus is constructed, in terms of role of mechanisms,
by a paper feeding portion, a conveying portion, a carriage
portion, a paper discharging portion, a cleaning portion and an
outer facing portion for protecting these portions and imparting
design feature.
FIG. 1 is a perspective view of the ink jet recording apparatus.
FIGS. 2 and 3 are drawings illustrating the internal mechanism of
the ink jet recording apparatus, in which FIG. 2 is a perspective
view from the top right-hand, and FIG. 3 is a sectional side
elevation of the ink jet recording apparatus.
Upon feeding of paper, only a predetermined number of recording
media is sent to a nip portion constructed by a paper feed roller
M2080 and a separating roller M2041 in the paper feeding portion
including a paper feeding tray M2060. The recording media are
separated in the nip portion, and only a recording medium located
uppermost is conveyed. The recording medium sent to the conveying
portion is guided to a pinch roller holder M3000 and a paper guide
flapper M3030 and sent to a pair of rollers of a conveying roller
M3060 and a pinch roller M3070. The pair of rollers having the
conveying roller M3060 and the pinch roller M3070 are rotated by
driving of an LF motor E0002, and the recording medium is conveyed
on a platen M3040 by this rotation.
Upon forming of an image on the recording medium, a recording head
H1001 (FIG. 4; detailed construction will be described
subsequently) is arranged at an intended image forming position in
the carriage portion, and an ink is ejected on the recording medium
according to a signal from an electric substrate E0014. While
conducting recording by the recording head H1001, a main scanning
in which a carriage M4000 scans in a column direction and a
secondary scanning in which the conveying roller M3060 conveys the
recording medium in a row direction are alternately repeated,
thereby forming an image on the recording medium. The recording
medium, on which the image has been formed, is nipped and conveyed
between a first paper discharging roller M3110 and a spur M3120 in
the paper discharging portion and discharged on a paper discharging
tray M3160.
In the cleaning portion, the recording head H1001 before and after
the recording is cleaned. A pump M5000 is operated with the
ejection orifices of the recording head H1001 being capped with a
cap M5010, whereby an unnecessary ink is sucked from the ejection
orifices of the recording head H1001. When the ink remaining in the
cap M5010 is sucked with the cap being opened, sticking of the
remaining ink or other troubles are prevented.
(Construction of Recording Head)
The construction of a head cartridge H1000 will be described. FIG.
4 illustrates the construction of the head cartridge H1000 and a
manner of installing an ink cartridge H1900 in the head cartridge
H1000. The head cartridge H1000 has a recording head H1001, a unit
for installing the ink cartridge H1900 and a unit for feeding an
ink from the ink cartridge H1900 to the recording head. The head
cartridge H1000 is detachably installed on the carriage M4000.
The ink jet recording apparatus forms an image with respective inks
of yellow, magenta, cyan, black, light magenta, light cyan and
green. Accordingly, ink cartridges H1900 for 7 colors are
independently provided. The ink according to the present invention
is used as at least one ink of the inks described above. As
illustrated in FIG. 4, each ink cartridge H1900 is detachably
installed in the head cartridge H1000. The ink cartridge H1900 can
be detached or installed with the head cartridge H1000 being
installed in the carriage M4000.
FIG. 5 is an exploded perspective view of the head cartridge H1000.
The head cartridge H1000 is constructed by recording element
substrates, plates, an electric wiring substrate H1300, a cartridge
holder H1500, a flow path forming member H1600, filters H1700 and
seal rubber H1800. The recording element substrates include a first
recording element substrate H1100 and a second recording element
substrate H1101, and the plates include a first plate H1200 and a
second plate H1400.
The first recording element substrate H1100 and the second
recording element substrate H1101 are Si substrates, and a
plurality of recording elements (nozzles) for ejecting an ink is
formed in one surfaces thereof by a photolithographic technique. An
electric wiring such as Al for supplying electric power to each
recording element is formed by a film forming technique. A
plurality of ink flow paths corresponding to the individual
recording elements is formed by the photolithographic technique.
Ink supply openings for supplying inks to a plurality of the ink
flow paths are formed so as to open to a back surface.
FIG. 6 is an enlarged elevational view illustrating the
constructions of the first recording element substrate H1100 and
the second recording element substrate H1101. Rows H2000 to H2600
(hereinafter also referred to as nozzle rows) of recording elements
for respectively supplying different inks are formed in the
substrates. In the first recording element substrate H1100, are
formed nozzle rows for 3 colors of a nozzle row H2000 for the
yellow ink, a nozzle row H2100 for the magenta ink and a nozzle row
H2200 for the cyan ink. In the second recording element substrate
H1101, are formed nozzle rows for 4 colors of a nozzle row H2300
for the light cyan ink, a nozzle row H2400 for the black ink, a
nozzle row H2500 for the green ink and a nozzle row H2600 for the
light magenta ink.
Each nozzle row is formed by 768 nozzles arranged at intervals of
1,200 dpi (dots/inch; referential value) in the conveying direction
(secondary scanning direction) of the recording medium. About 2
picoliters of an ink are ejected from each nozzle. The opening area
in each ejection orifice is thus set to about 100 .mu.m.sup.2.
Description is given with reference to FIGS. 4 and 5. The first
recording element substrate H1100 and second recording element
substrate H1101 are bonded and fixed to the first plate H1200. In
the first plate, are formed ink supply openings H1201 for supplying
inks to the first recording element substrate H1100 and second
recording element substrate H1101. Further, the second plate H1400
having openings is bonded and fixed to the first plate H1200. This
second plate H1400 holds the electric wiring substrate H1300 so as
to electrically connect the electric wiring substrate H1300 to the
first recording element substrate H1100 and second recording
element substrate H1101.
The electric wiring substrate H1300 applies an electric signal for
ejecting the ink from each nozzle formed in the first recording
element substrate H1100 and second recording element substrate
H1101. The electric wiring substrate H1300 has electric wirings
corresponding to the first recording element substrate H1100 and
second recording element substrate H1101, and an external signal
input terminal H1301 located at edges of the electric wirings for
receiving electric signals from the ink jet recording apparatus.
The external signal input terminal H1301 is positioned and fixed on
the back surface side of the cartridge holder H1500.
The flow path forming member H1600 is fixed to the cartridge holder
H1500 for holding the ink cartridges H1900 by, for example,
ultrasonic welding to form ink flow paths H1501 linking from the
ink cartridges H1900 to the first plate H1200. The filters H1700
are provided at ends on the ink cartridge side of the ink flow
paths H1501 linking to the ink cartridges H1900 so as to prevent
invasion of dust from the outside. Sealing rubbers H1800 are fitted
to portions engaged with the ink cartridges H1900 so as to prevent
evaporation of the inks from the engaged portions.
A cartridge holder portion is bonded to a recording head portion
H1001 by, for example, adhesion as described above, thereby forming
the head cartridge H1000. The cartridge holder portion is
constructed by the cartridge holder H1500, the flow path forming
member H1600, the filters H1700 and the sealing rubber H1800. The
recording head portion H1001 is constructed by the first recording
element substrate H1100, the second recording element substrate
H1101, the first plate H1200, the electric wiring substrate H1300
and the second plate H1400.
The recording head of the thermal ink jet system that recording is
conducted using electrothermal converters (recording elements),
which generate thermal energy for causing an ink to cause film
boiling corresponding to an electric signal, has been described as
an embodiment of the recording head herein. The typical
construction and principle thereof are those which perform
recording by using fundamental principles as disclosed in, for
example, U.S. Pat. Nos. 4,723,129 and 4,740,796. This system is
applicable to any of what are called an On-Demand type and a
continuous type.
In particular, the thermal ink jet system is effectively applied to
the On-Demand type. In the case of the On-Demand type, at least one
driving signal, which corresponds to recording information and
gives a rapid temperature rise exceeding nuclear boiling, is
applied to an electrothermal converter arranged corresponding to a
liquid flow path, in which an ink is retained, thereby causing the
electrothermal converter to generate thermal energy to cause film
boiling in the ink. As a result, a bubble can be formed in the ink
in response to the driving signal in relation of one to one. The
ink is ejected through an ejection orifice by the
growth-contraction of this bubble to form at least one droplet.
When the driving signal is applied in the form of a pulse, the
growth-contraction of the bubble is suitably conducted in a moment,
so that the ejection of the ink excellent in responsiveness in
particular can be achieved. It is therefore favorable to use such
pulsed signals.
The ink according to the present invention may also be favorably
used in an ink jet recording apparatus utilizing mechanical energy
as will be described below, not limited to the above-described
thermal ink jet system. The ink jet recording apparatus of such a
system is equipped with a nozzle-forming substrate having a
plurality of nozzles, pressure-generating elements arranged in an
opposing relation to the nozzles and each composed of a
piezoelectric material and an electrically conductive material, and
an ink filled around the pressure-generating elements, in which the
pressure-generating elements are displaced by voltage applied to
eject the ink from the nozzles.
The ink jet recording apparatus are not limited to the apparatus as
described above in which the head and the ink cartridge are
separately provided. Therefore, a device in which these members are
integrally formed may also be used. The ink cartridge may be
separably or unseparably and integrally installed in a recording
head and mounted on a carriage, or may be provided at a fixing site
of an ink jet recording apparatus to supply an ink to a recording
head through an ink supply member such as a tube. When construction
for applying a favorable negative pressure to a recording head is
provided in the ink cartridge, the following construction may be
used. More specifically, examples thereof include a mode in which
an absorbing member is arranged in an ink storage portion of the
ink cartridge, and a mode having a flexible ink-storing bag and a
spring part for applying biasing force to the bag in a direction to
expand the internal volume of the bag. The ink jet recording
apparatus may use a recording system of such serial type as
described above, or a line printer type in which recording elements
are arranged over a range corresponding to the overall width of a
recording medium.
EXAMPLES
The present invention will hereinafter be described in more detail
by the following Examples and Comparative Examples. However, the
present invention is not limited to the following examples unless
going beyond the gist of the present invention. Incidentally, parts
or % in the preparation of the coloring materials or the ink mean
"parts or % by mass" unless expressly noted.
<Preparation of Coloring Material>
All compounds of the general formula (I) obtained by syntheses of
coloring materials described below are mixtures, and a mixture of
the following isomers is described as "a compound" unless expressly
noted. More specifically, the compound includes regioisomers of the
compound, regioisomers with respect to the nitrogen atom(s) in a
nitrogen-containing aromatic heterocyclic ring, isomers with
respect to the ratio of the benzene ring/the nitrogen-containing
aromatic heterocyclic ring among A, B, C and D in the general
formula (I), and .alpha./.beta.-regioisomers with respect to the
substituted or unsubstituted sulfamoyl group in the benzene ring.
As described above, it is extremely difficult to isolate a specific
compound from a mixture of these isomers and determine the
structure thereof, and so an example among thinkable isomers is
taken as a representative example for the sake of convenience, and
the structural formula thereof is described. With respect to
compounds obtained upon synthesis of the compound of the general
formula (I), mass spectrometric analysis, ICP emission spectrometry
and analysis by absorbance measurement were conducted to confirm
the syntheses of the respective compounds.
(Mass Spectrometric Analysis)
With respect to the respective compounds, DI-MS (direct mass
spectrometry) was conducted. Analytic conditions of DI-MS are as
follows. EI method Mass spectrometer: SSQ-7000 Ion source
temperature: 230.degree. C. Degree of vacuum: about 8 mT.
(ICP Emission Spectrometry)
With respect to the respective compounds containing copper, the
content of copper was analyzed. Specifically, the analysis was
conducted in the following manner. After about 1 g of a sample for
analysis was precisely weighed, and this sample was dissolved in
pure water, the resultant solution was quantified in a 100-mL
messflask. After 0.1 mL of this solution was taken and put in a
50-mL messflask by means of a whole pipette, a certain amount of Y
(yttrium) was added as an internal standard substance, and the
volume was quantified to 50 mL with pure water. Incidentally, the
apparatus used at this time is an ICP emission spectral apparatus
SPS3100 (manufactured by SII Nano Technology Inc.).
(Absorbance Measurement)
With respect to the respective compounds, the absorbance was
measured. Measuring conditions of the absorbance are shown below.
Spectrophotometer: automatic recording spectrophotometer (trade
name: U-3300, manufactured by Hitachi Ltd.) Measuring cell: 1-cm
quartz cell Sampling interval: 0.1 nm Scanning speed: 30 nm/min.
Number of measurements: 5 measurements to be averaged.
Compounds 1-1 to 1-7 that are the first coloring material used in
Examples, and Compound 2 were respectively synthesized in the
following manner. Comparative Compound 1 that is a cyan dye used in
Comparative Examples was also synthesized.
[Synthesis of Compound 1-1]
(1) Synthesis of Compound (1):
##STR00043##
LOTAT OH104-K (product of Lion Corporation; 7.2 parts) and cyanuric
chloride (239.9 parts) were added into ice water (2,000 parts), and
the mixture was stirred for 30 minutes. Monosodium
aniline-2,5-disulfonate (purity: 91.2%, 411.6 parts) was added to
this mixture, and the pH of the reaction liquid was kept at 2.7 to
3.0 while adding a 25% aqueous solution of sodium hydroxide,
thereby conducting a reaction for 1 hour at 10 to 15.degree. C. and
then for 2 hours at 27 to 30.degree. C. After the reaction liquid
was then cooled to 10.degree. C. or less, a 25% aqueous solution of
sodium hydroxide was added to adjust the pH of the reaction liquid
to 7.0 to 7.5. To this reaction liquid was added 28% aqueous
ammonia (118.4 parts), and the resultant mixture was held for 3
hours at a temperature of 10 to 15.degree. C. and a pH of 9.5 to
10.0. Thereafter, concentrated hydrochloric acid was added to
adjust the pH of the reaction liquid to 6.0 to 7.0. Ice (2,000
parts) was then added to cool the reaction liquid to 0.degree. C.,
and ethylenediamine (780 parts) was added dropwise while keeping
the temperature at 5.degree. C. or less. Thereafter, the
temperature of the reaction liquid was controlled to 10 to
15.degree. C. and held for 1 hour. Concentrated hydrochloric acid
was then added dropwise to this reaction liquid to adjust the pH of
the reaction liquid to 0.9 to 1.0, during which ice was added so as
not to raise the temperature, thereby keeping the temperature of
the reaction liquid at 10 to 15.degree. C. Ice was additionally
added to this reaction liquid to lower the temperature of the
reaction liquid to 10.degree. C. or less. The amount of the
reaction liquid at this time was 13,000 parts. Sodium chloride
(2,600 parts; 20% to the amount of the reaction liquid) was added
to the reaction liquid, and the resultant mixture was stirred for 1
hour to deposit crystals. The crystals deposited were taken out by
filtration and washed with a 20% aqueous solution (3,000 parts) of
sodium chloride to obtain a wet cake (743.0 parts; purity: 59.3%,
HPLC purity: 93.3%).
(2) Synthesis of copper tribenzo(2,3-pyrido)porphyrazine [the
following Compound (2): a mixture in which one of A, B, C and D in
the general formula (A) is a pyridine ring, and the remainder are
benzene rings]:
##STR00044##
Sulfolane (250 parts), phthalimide (22.1 parts), quinolinic acid
(8.4 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added into a 4-necked flask, and the reaction liquid was heated to
200.degree. C. and held for 5 hours. After completion of the
reaction, the reaction liquid was cooled to 75.degree. C., methanol
(200 parts) was added, and crystals deposited were separated by
filtration. The resultant crystals were washed with methanol (250
parts) and then with warm water (500 parts) to obtain a wet cake
(61.9 parts). The resultant wet cake was added to 5% hydrochloric
acid (500 parts), and this liquid was heated to 60.degree. C. and
held for 1 hour. The resultant crystals were separated by
filtration and washed with water (300 parts). The resultant wet
cake was then added to 10% aqueous ammonia (500 parts), and the
temperature of the liquid was controlled to 25 to 30.degree. C. and
held for 1 hour. Thereafter, the resultant crystals were separated
by filtration and then washed with water (300 parts) to obtain a
wet cake (64.9 parts). The wet cake thus obtained was dried at
80.degree. C. to obtain blue crystals (20.9 parts). The blue
crystals were analyzed. As a result, the following measured values
were obtained. From these results, the resultant blue crystals were
identified as Compound (2) having the above structure.
Maximum absorption wavelength (.lamda..sub.max): 670.5 nm (in
pyridine)
TABLE-US-00005 Result of elemental analysis:
C.sub.31H.sub.15N.sub.9Cu C H N Cu Calculated (%) 64.52 2.62 21.85
11.01 Found (%) 63.80 2.79 20.59 10.92
(3) Synthesis of copper tribenzo(2,3-pyrido)porphyrazine
tri(sulfonyl chloride) [the following Compound (3): a mixture in
which one of outermost aromatic rings of a main component in the
mixture is a pyridine ring, and the remaining 3 rings are benzene
rings]:
##STR00045##
Copper tribenzo(2,3-pyrido)porphyrazine (5.8 parts) obtained in the
step (2) was gradually added to chlorosulfonic acid (46.2 parts)
under stirring while keeping the temperature of the liquid at
60.degree. C. or less. Thereafter, a reaction was conducted for 4
hours at 140.degree. C. The reaction liquid was then cooled to
70.degree. C., and thionyl chloride (17.9 parts) was added dropwise
over 30 minutes to conduct a reaction for 3 hours at 70.degree. C.
The reaction liquid was cooled to 30.degree. C. or less and slowly
poured into ice water (500 parts), and crystals deposited were
separated by filtration and washed with cold water (200 parts) to
obtain a wet cake (71.1 parts) of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride).
(4) Synthesis of the following Compound (4) [a mixture containing
Exemplified Compound I-1: a mixture in which one of outermost
aromatic rings of a main component in the mixture is a pyridine
ring, the remaining 3 rings are benzene rings, b is 2.4, and c is
0.6]:
##STR00046##
The wet cake (71.1 parts) of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride) (Compound
(3)) obtained in the step (3) was added into ice water (200 parts)
and suspended under stirring. A solution of Compound (1) (purity:
59.3%, 20.5 parts) obtained in the step (1) dissolved in aqueous
ammonia (3.0 parts) and warm water (100 parts) was then added to
the suspension. The pH of the reaction liquid was kept at 9.0 to
9.3 by adding 28% aqueous ammonia thereto, and the temperature of
the reaction liquid was controlled to 17 to 20.degree. C. to
conduct a reaction for 6 hours. Thereafter, the reaction liquid was
heated to 60.degree. C. The amount of the reaction liquid at this
time was 500 parts. Sodium chloride (100 parts, 20% to the amount
of the reaction liquid) was added to this reaction liquid, and 35%
aqueous hydrochloric acid was added to adjust the pH of the
reaction liquid to 1.0, thereby depositing crystals. The crystals
deposited were separated by filtration and washed with a 20%
aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (47.7 parts). After the resultant wet cake was dissolved in
water again, and the pH of the resultant solution was adjusted to
9.0, the whole amount was controlled to 300 parts, and the
temperature of the solution was raised to 60.degree. C. The amount
of the solution at this time was 320 parts. Sodium chloride (48
parts, 15% to the amount of the solution) was added to the
solution, and 35% aqueous hydrochloric acid was added to adjust the
pH of the solution to 1.0, thereby depositing crystals. The
crystals deposited were separated by filtration and washed with a
15% aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (47.8 parts). After the resultant wet cake (47.8 parts) was
added into methanol (250 parts) and the resultant mixture was
stirred for 1 hour at 60.degree. C. to suspend the wet cake,
filtration, washing with methanol (100 parts) and drying were
conducted to obtain blue crystals (Compound (4), 10.7 parts). The
blue crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) was 611 nm (in an aqueous solution).
The resultant Compound (4) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-1 of a
sodium salt type.
[Synthesis of Compound 1-2]
(1) Synthesis of copper dibenzobis(2,3-pyrido)-porphyrazine [the
following Compound (5): a mixture in which two of A, B, C and D in
the general formula (A) are pyridine rings, and the remainder are
benzene rings]:
##STR00047##
Sulfolane (250 parts), phthalimide (14.7 parts), quinolinic acid
(16.7 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added into a 4-necked flask, and the reaction liquid was heated to
200.degree. C. and held for 5 hours. After completion of the
reaction, the reaction liquid was cooled to 85.degree. C., methanol
(200 parts) was added, and crystals deposited were separated by
filtration. The resultant crystals were washed with methanol (200
parts) and then with warm water (500 parts), and then dried to
obtain crude copper dibenzobis(2,3-pyrido)porphyrazine (mixture,
24.1 parts) as blue crystals. The resultant crude copper
dibenzobis(2,3-pyrido)porphyrazine (mixture, 24.1 parts) was added
into 5% aqueous hydrochloric acid (500 parts), and this liquid was
heated to 60.degree. C. and held for 1 hour. Thereafter, the
crystals were separated by filtration and then washed with water
(100 parts) to obtain a wet cake. The resultant wet cake was added
into 10% aqueous ammonia (500 parts), and the temperature of the
liquid was controlled to 25 to 30.degree. C. and held for 1 hour.
The resultant crystals were separated by filtration and then washed
with water (200 parts) to obtain a wet cake (44.4 parts). The
resultant wet cake was dried at 80.degree. C. to obtain copper
dibenzobis(2,3-pyrido)porphyrazine (mixture, 17.7 parts) as blue
crystals. The blue crystals were analyzed. As a result, the
following measured values were obtained. From these results, the
resultant blue crystals were identified as Compound (5) having the
above structure.
Maximum absorption wavelength (.lamda..sub.max): 662.5 nm (in
pyridine)
TABLE-US-00006 Result of elemental analysis:
C.sub.30H.sub.14N.sub.10Cu C H N Cu Calculated (%) 62.33 2.44 24.23
10.99 Found (%) 61.46 2.62 23.35 10.37
(2) Synthesis of copper dibenzobis(2,3-pyrido)-porphyrazine
di(sulfonyl chloride) [the following Compound (6): a mixture in
which two of outermost aromatic rings of a main component in the
mixture are pyridine rings, and the remaining 2 rings are benzene
rings]:
##STR00048##
Copper dibenzobis(2,3-pyrido)porphyrazine (5.8 parts) obtained in
the step (1) was gradually added to chlorosulfonic acid (46.2
parts) under stirring while keeping the temperature of the liquid
at 60.degree. C. or less. Thereafter, a reaction was conducted for
4 hours at 140.degree. C. The reaction liquid was then cooled to
70.degree. C., and thionyl chloride (17.9 parts) was added dropwise
over 30 minutes to conduct a reaction for 3 hours at 70.degree. C.
The reaction liquid was cooled to 30.degree. C. or less and slowly
poured into ice water (500 parts), and crystals deposited were
separated by filtration and washed with cold water (200 parts) to
obtain a wet cake (46.0 parts) of copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride).
(3) Synthesis of the following Compound (7) [a mixture containing
Exemplified Compounds I-2 and I-3: a mixture in which two of
outermost aromatic rings of a main component in the mixture are
pyridine rings, the remaining 2 rings are benzene rings, b is 1.6,
and c is 0.4]:
##STR00049##
The wet cake (46.0 parts) of copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride) (Compound
(6)) obtained in the step (2) was added into ice water (250 parts)
and suspended under stirring. A solution of Compound (1) (purity:
59.3%, 20.5 parts) obtained upon the synthesis of Compound 1-1
dissolved in aqueous ammonia (4.0 parts) and warm water (100 parts)
was then added to the suspension. The pH of the reaction liquid was
kept at 9.0 to 9.3 by adding 28% aqueous ammonia thereto, and the
temperature of the reaction liquid was controlled to 17 to
20.degree. C. to conduct a reaction for 4 hours. Thereafter, the
reaction liquid was heated to 60.degree. C. The amount of the
reaction liquid at this time was 480 parts. Sodium chloride (48
parts, 10% to the amount of the reaction liquid) was added to this
reaction liquid, and 35% aqueous hydrochloric acid was added to
adjust the pH of the reaction liquid to 1.0, thereby depositing
crystals. The crystals deposited were separated by filtration and
washed with a 15% aqueous solution (100 parts) of sodium chloride
to obtain a wet cake (86.1 parts). After the resultant wet cake was
dissolved in water again, and the pH of the resultant solution was
adjusted to 9.0, the whole amount was controlled to 400 parts, and
the temperature of the solution was raised to 60.degree. C. The
amount of the solution at this time was 410 parts. Sodium chloride
(41 parts, 10% to the amount of the solution) was added to the
solution, and 35% aqueous hydrochloric acid was added to adjust the
pH of the solution to 1.0, thereby depositing crystals. The
crystals deposited were separated by filtration and washed with a
10% aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (65.7 parts). After the resultant wet cake (65.7 parts) was
added into methanol (330 parts) and the resultant mixture was
stirred for 1 hour at 60.degree. C. to suspend the wet cake,
filtration, washing with methanol (100 parts) and drying were
conducted to obtain blue crystals (Compound (7), 9.3 parts). The
blue crystals were analyzed. As a result, a maximum absorption
wavelength (.lamda..sub.max) was 602 nm (in an aqueous solution).
The resultant Compound (7) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-2 of a
sodium salt type.
[Synthesis of Compound 1-3]
(1) Synthesis of copper benzotris(2,3-pyrido)porphyrazine [the
following Compound (8): a mixture in which three of A, B, C and D
in the general formula (A) are pyridine rings, and the remainder is
a benzene ring]:
##STR00050##
Sulfolane (250 parts), phthalimide (7.4 parts), quinolinic acid
(25.1 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added into a 4-necked flask, and the reaction liquid was heated to
200.degree. C. and held for 5 hours. After completion of the
reaction, the reaction liquid was cooled to 70.degree. C., methanol
(200 parts) was added, and crystals deposited were separated by
filtration. The resultant crystals were washed with methanol (200
parts) and then with warm water (500 parts), and then dried to
obtain crude copper benzotris(2,3-pyrido)porphyrazine (mixture,
20.5 parts) as blue crystals. The resultant crude copper
benzotris(2,3-pyrido)porphyrazine (mixture, 14.5 parts) was added
into 5% hydrochloric acid (500 parts), and this liquid was heated
to 60.degree. C. and held for 1 hour. Thereafter, the crystals were
separated by filtration and then washed with water (100 parts) to
obtain a wet cake. The resultant wet cake was added into 10%
aqueous ammonia (500 parts), and the temperature of the liquid was
controlled to 25 to 30.degree. C. and held for 1 hour. The
resultant crystals were separated by filtration and then washed
with water (100 parts) to obtain a wet cake (23.5 parts). The
resultant wet cake was dried at 80.degree. C. to obtain copper
benzotris(2,3-pyrido)porphyrazine (mixture, 9.7 parts) as blue
crystals. The blue crystals were analyzed. As a result, the
following measured values were obtained. From these results, the
resultant blue crystals were identified as Compound (8) having the
above structure.
.lamda..sub.max: 655 nm (in pyridine)
TABLE-US-00007 Elemental analysis: C.sub.29H.sub.13N.sub.11Cu C H N
Cu Calculated (%) 60.15 2.26 26.60 10.97 Found (%) 58.73 2.48 25.87
10.08
(2) Synthesis of copper benzotris(2,3-pyrido)-porphyrazine
di(sulfonyl chloride) [the following Compound (9): a mixture in
which three of outermost aromatic rings of a main component in the
mixture are pyridine rings, and the remainder is a benzene
ring]:
##STR00051##
Copper benzotris(2,3-pyrido)porphyrazine (5.8 parts) obtained in
the step (1) was gradually added to chlorosulfonic acid (46.2
parts) under stirring while keeping the temperature of the liquid
at 60.degree. C. or less. Thereafter, a reaction was conducted for
4 hours at 140.degree. C. The reaction liquid was then cooled to
70.degree. C., and thionyl chloride (17.9 parts) was added dropwise
over 30 minutes to conduct a reaction for 3 hours at 70.degree. C.
The reaction liquid was cooled to 30.degree. C. or less and slowly
poured into ice water (500 parts), and crystals deposited were
separated by filtration and washed with cold water (200 parts) to
obtain a wet cake (33.0 parts) of copper
benzotris(2,3-pyrido)porphyrazine di(sulfonyl chloride).
(3) Synthesis of the following Compound (10) [a mixture in which
three of outermost aromatic rings of a main component in the
mixture are pyridine rings, the remainder is a benzene ring, b is
0.9, and c is 0.1]:
##STR00052##
The wet cake (33.0 parts) of copper
benzotris(2,3-pyrido)porphyrazine di(sulfonyl chloride) (Compound
(9)) obtained in the step (2) was added into ice water (250 parts)
and suspended under stirring. A solution of Compound (1) (purity:
59.3%, 20.5 parts) obtained upon the synthesis of Compound 1-1
dissolved in aqueous ammonia (4.0 parts) and warm water (90 parts)
was then added to the suspension. The pH of the reaction liquid was
kept at 9.0 to 9.3 by adding 28% aqueous ammonia thereto, and the
temperature of the reaction liquid was controlled to 17 to
20.degree. C. to conduct a reaction for 3 hours. Thereafter, the
reaction liquid was heated to 60.degree. C. The amount of the
reaction liquid at this time was 450 parts. Sodium chloride (67.5
parts, 15% to the amount of the reaction liquid) was added to this
reaction liquid, and 35% aqueous hydrochloric acid was added to
adjust the pH of the reaction liquid to 1.0, thereby depositing
crystals. The crystals deposited were separated by filtration and
washed with a 15% aqueous solution (100 parts) of sodium chloride
to obtain a wet cake (42.6 parts). After the resultant wet cake was
dissolved in water again, and the pH of the resultant solution was
adjusted to 9.0, the whole amount was controlled to 300 parts, and
the temperature of the solution was raised to 60.degree. C. The
amount of the solution at this time was 310 parts. Sodium chloride
(31 parts, 10% to the amount of the solution) was added to the
solution, and 35% aqueous hydrochloric acid was added to adjust the
pH of the solution to 1.0, thereby depositing crystals. The
crystals deposited were separated by filtration and washed with a
10% aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (42.8 parts). After the resultant wet cake (42.8 parts) was
added into methanol (220 parts) and the resultant mixture was
stirred for 1 hour at 60.degree. C. to suspend the wet cake,
filtration, washing with methanol (100 parts) and drying were
conducted to obtain blue crystals (Compound (10), 5.0 parts). The
blue crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) was 584 nm (in an aqueous solution).
The resultant Compound (10) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-3 of a
sodium salt type.
[Synthesis of Compound 1-4]
(1) Synthesis of copper tribenzo(2,3-pyrido)porphyrazine tri(sodium
sulfate) [the following Compound (11): sodium salt of a mixture in
which one of outermost aromatic rings of a main component in the
mixture is a pyridine ring, and the remainder are benzene
rings]:
##STR00053##
Sulfolane (250 parts), 4-sulfophthalic acid (50% aqueous solution
containing 20% of 3-sulfophthalic acid, product of Pilot Chemical;
73.8 parts) and 28% aqueous ammonia (27.3 parts) were added into a
4-necked flask, and the reaction liquid was heated to 160.degree.
C. while distilling off water. After completion of the reaction,
the reaction liquid was cooled to 100.degree. C., quinolinic acid
(8.4 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added, and the resultant mixture was heated to 200.degree. C. and
held for 5 hours. After completion of the reaction, the reaction
liquid was cooled to 90.degree. C., methanol (200 parts) was added,
and crystals deposited were separated by filtration. The resultant
crystals were washed with methanol (750 parts) to obtain a wet
cake. The resultant wet cake was added into a mixed liquid of 28.6%
brine (900 parts) and concentrated hydrochloric acid (100 parts),
and the liquid was heated to 60.degree. C. and held for 1 hour. The
resultant crystals were separated by filtration and then washed
with a mixed liquid of 28.6% brine (225 parts) and concentrated
hydrochloric acid (25 parts). The resultant wet cake was then added
into methanol (500 parts), 28% aqueous ammonia (50 parts) was
further added, the liquid was heated to 60.degree. C. and held for
1 hour, and the resultant crystals were separated by filtration and
washed with methanol (200 parts) to obtain a wet cake (78.1 parts).
The resultant wet cake was added into methanol (500 parts), a 25%
aqueous solution (30 parts) of sodium hydroxide was added, the
liquid was heated to 60.degree. C. and held for 1 hour, and the
resultant crystals were separated by filtration and washed with
methanol (200 parts) to obtain a wet cake (72.6 parts). The
resultant wet cake was dried at 80.degree. C. to obtain copper
tribenzo(2,3-pyrido)porphyrazine tri(sodium sulfonate) (32.4 parts)
as blue crystals. The blue crystals were analyzed. As a result, the
maximum absorption wavelength (.lamda..sub.max) thereof was 625 nm
(in an aqueous solution). From this result, the resultant blue
crystals were identified as Compound (11) having the above
structure.
(2) Synthesis of copper tribenzo(2,3-pyrido)porphyrazine
tri(sulfonyl chloride) [the following Compound (12): a mixture that
one of outermost aromatic rings of a main component in the mixture
is a pyridine ring, and the remainder are benzene rings]:
##STR00054##
Copper tribenzo(2,3-pyrido)porphyrazine tri-(sodium sulfate) (8.8
parts) obtained in the step (1) was gradually added to
chlorosulfonic acid (70.6 parts) under stirring while keeping the
temperature of the liquid at 60.degree. C. or less. Thereafter, a
reaction was conducted for 4 hours at 120.degree. C. The reaction
liquid was then cooled to 70.degree. C., and thionyl chloride (17.9
parts) was added dropwise over 30 minutes to conduct a reaction for
3 hours at 70.degree. C. The reaction liquid was cooled to
30.degree. C. or less and slowly poured into ice water (500 parts),
and crystals deposited were separated by filtration and washed with
cold water (100 parts) to obtain a wet cake (61.2 parts) of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride)
(mixture).
(3) Synthesis of the following Compound (13) [a mixture containing
Exemplified Compound I-1: a mixture in which one of outermost
aromatic rings of a main component in the mixture is a pyridine
ring, the remainder are benzene rings, b is 2, and c is 1]:
##STR00055##
The wet cake (61.2 parts) of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride) (Compound
(12)) obtained in the step (2) was added into ice water (250 parts)
and suspended under stirring. A solution of Compound (1) (purity:
59.3%, 20.5 parts) obtained upon the synthesis of Compound 1-1
dissolved in aqueous ammonia (3.0 parts) and warm water (90 parts)
was then added to the suspension. The pH of the reaction liquid was
kept at 9.0 to 9.3 by adding 28% aqueous ammonia thereto, and the
temperature of the reaction liquid was controlled to 17 to
20.degree. C. to conduct a reaction for 4 hours. Thereafter, the
reaction liquid was heated to 60.degree. C. The amount of the
reaction liquid at this time was 500 parts. Sodium chloride (100
parts, 20% to the amount of the reaction liquid) was added to this
reaction liquid, and 35% aqueous hydrochloric acid was added to
adjust the pH of the reaction liquid to 1.0, thereby depositing
crystals. The crystals deposited were separated by filtration and
washed with a 20% aqueous solution (100 parts) of sodium chloride
to obtain a wet cake (37.0 parts). After the resultant wet cake was
dissolved in water again, and the pH of the resultant solution was
adjusted to 9.0, the whole amount was controlled to 400 parts, and
the temperature of the solution was raised to 60.degree. C. The
amount of the solution at this time was 400 parts. Sodium chloride
(80 parts, 20% to the amount of the solution) was added to the
solution, and 35% hydrochloric acid was added to adjust the pH of
the solution to 1.0, thereby depositing crystals. The crystals
deposited were separated by filtration and washed with a 20%
aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (39.2 parts). After the resultant wet cake (39.2 parts) was
added into methanol (200 parts) and the resultant mixture was
stirred for 1 hour at 60.degree. C. to suspend the wet cake,
filtration, washing with methanol (200 parts) and drying were
conducted to obtain blue crystals (Compound (13), 9.8 parts). The
blue crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) was 614 nm (in an aqueous solution).
The resultant Compound (13) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-4 of a
sodium salt type.
[Synthesis of Compound 1-5]
(1) Synthesis of copper dibenzobis(2,3-pyrido)-porphyrazine
di(sodium sulfate) [the following Compound (14): sodium salt of a
mixture in which two of outermost aromatic rings of a main
component in the mixture are pyridine rings, and the remainder are
benzene rings]:
##STR00056##
Sulfolane (250 parts), 4-sulfophthalic acid (50% aqueous solution
containing 20% of 3-sulfophthalic acid, product of Pilot Chemical;
49.2 parts) and 28% aqueous ammonia (18.2 parts) were added into a
4-necked flask, and the reaction liquid was heated to 160.degree.
C. while distilling off water. After completion of the reaction,
the reaction liquid was cooled to 110.degree. C., quinolinic acid
(16.7 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added, and the resultant mixture was heated to 200.degree. C. and
held for 5 hours. After completion of the reaction, the reaction
liquid was cooled to 70.degree. C., methanol (100 parts) was added,
and crystals deposited were separated by filtration. The resultant
crystals were washed with methanol (150 parts) and then dried to
obtain blue crystals (36.9 parts). The resultant blue crystals were
added into a mixed liquid of 20% brine (1,000 parts) and
concentrated hydrochloric acid (10 parts), and the liquid was
heated to 60.degree. C. and held for 1 hour. Thereafter, a 25%
aqueous solution of sodium hydroxide was added to adjust the pH of
the liquid to 7 to 8, and crystals deposited were separated by
filtration to obtain a wet cake. The resultant wet cake was added
into water (1,000 parts), the temperature of the liquid was
controlled to 60.degree. C. and held for 1 hour, and methanol (600
parts) was added to deposit crystals. The resultant crystals were
separated by filtration and then washed with methanol (100 parts)
to obtain a wet cake (110.7 parts). The resultant wet cake was
dried at 80.degree. C. to obtain copper
dibenzobis(2,3-pyrido)porphyrazine di(sodium sulfonate) (28.9
parts) as blue crystals. The blue crystals were analyzed. As a
result, the maximum absorption wavelength (.lamda..sub.max) thereof
was 607.5 nm (in an aqueous solution). From this result, the
resultant blue crystals were identified as Compound (14) having the
above structure.
(2) Synthesis of copper dibenzobis(2,3-pyrido)porphyrazine
di(sulfonyl chloride) [the following Compound (15): a mixture in
which two of outermost aromatic rings of a main component in the
mixture are pyridine rings, and the remainder are benzene
rings]:
##STR00057##
Copper dibenzobis(2,3-pyrido)porphyrazine di-(sodium sulfate) (7.8
parts) obtained in the step (1) was gradually added to
chlorosulfonic acid (62.6 parts) under stirring while keeping the
temperature of the liquid at 60.degree. C. or less. Thereafter, a
reaction was conducted for 4 hours at 120.degree. C. The reaction
liquid was then cooled to 70.degree. C., and thionyl chloride (17.9
parts) was added dropwise over 30 minutes to conduct a reaction for
3 hours at 70.degree. C. The reaction liquid was cooled to
30.degree. C. or less and slowly poured into ice water (500 parts),
and crystals deposited were separated by filtration and washed with
cold water (200 parts) to obtain a wet cake (44.3 parts) of copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride).
(3) Synthesis of the following Compound (16) [a mixture containing
Exemplified Compounds I-2 and I-3: a mixture in which two of
outermost aromatic rings of a main component in the mixture are
pyridine rings, the remainder are benzene rings, b is 1.7, and c is
0.3]:
##STR00058##
The wet cake (44.3 parts) of copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride) (Compound
(15)) obtained in the step (2) was added into ice water (250 parts)
and suspended under stirring. A solution of Compound (1) (purity:
59.3%, 25.3 parts) obtained upon the synthesis of Compound 1-1
dissolved in aqueous ammonia (5.0 parts) and warm water (100 parts)
was then added to the suspension. The pH of the reaction liquid was
kept at 9.0 to 9.3 by adding 28% aqueous ammonia thereto, and the
temperature of the reaction liquid was controlled to 17 to
20.degree. C. to conduct a reaction for 3 hours. Thereafter, the
reaction liquid was heated to 60.degree. C. The amount of the
reaction liquid at this time was 520 parts. Sodium chloride (104
parts, 20% to the amount of the reaction liquid) was added to this
reaction liquid, and 35% hydrochloric acid was added to adjust the
pH of the reaction liquid to 1.0, thereby depositing crystals. The
crystals deposited were separated by filtration and washed with a
20% aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (27.6 parts). After the resultant wet cake was dissolved in
water again, and the pH of the resultant solution was adjusted to
9.0, the whole amount was controlled to 300 parts, and the
temperature of the solution was raised to 60.degree. C. The amount
of the solution at this time was 310 parts. Sodium chloride (62
parts, 20% to the amount of the solution) was added to the
solution, and 35% aqueous hydrochloric acid was added to adjust the
pH of the solution to 1.0, thereby depositing crystals. The
crystals deposited were separated by filtration and washed with a
20% aqueous solution (100 parts) of sodium chloride to obtain a wet
cake (32.0 parts). After the resultant wet cake (32.0 parts) was
added into methanol (160 parts) and the resultant mixture was
stirred for 1 hour at 60.degree. C. to suspend the wet cake,
filtration, washing with methanol (100 parts) and drying were
conducted to obtain blue crystals (Compound (16), 7.6 parts). The
blue crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) was 609 nm (in an aqueous solution).
The resultant Compound (16) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-5 of a
sodium salt type.
[Synthesis of Compound 1-6]
(1) Synthesis of copper dibenzobis(2,3-pyrazino)-porphyrazine
di(sodium sulfate) [the following Compound (17): sodium salt of a
mixture in which two of outermost aromatic rings of a main
component in the mixture are pyrazine rings, and the remainder are
benzene rings]:
##STR00059##
Sulfolane (250 parts), 4-sulfophthalic acid (50% aqueous solution
containing 20% of 3-sulfophthalic acid, product of Pilot Chemical;
49.2 parts) and 28% aqueous ammonia (18.2 parts) were added into a
4-necked flask, and the reaction liquid was heated to 160.degree.
C. while distilling off water. After completion of the reaction,
the reaction liquid was cooled to 100.degree. C.,
pyrazinedicarboxylic acid (16.8 parts), urea (72.0 parts),
copper(II) chloride dihydrate (purity: 97.0%; 8.8 parts) and
ammonium molybdate (1.0 part) were added, and the resultant mixture
was heated to 200.degree. C. and held for 5 hours. After completion
of the reaction, the reaction liquid was cooled to 70.degree. C.,
methanol (100 parts) was added, and crystals deposited were
separated by filtration. The resultant crystals were washed with
methanol (400 parts) to obtain a wet cake (55.0 parts). The
resultant wet cake was added into a mixed liquid of 28.6% brine
(900 parts) and concentrated hydrochloric acid (100 parts), and the
liquid was heated to 60.degree. C. and held for 1 hour. The
resultant crystals were separated by filtration and then washed
with a mixed liquid of 28.6% brine (225 parts) and concentrated
hydrochloric acid (25 parts). The resultant wet cake was then added
into methanol (500 parts), 28% aqueous ammonia (50 parts) was
further added, the liquid was heated to 6.degree. C. and held for 1
hour, and crystals were separated by filtration and washed with
methanol (200 parts) to obtain a wet cake (34.8 parts). The
resultant wet cake was added into methanol (500 parts), a 25%
aqueous solution (30 parts) of sodium hydroxide was added, the
liquid was heated to 60.degree. C. and held for 1 hour, and
crystals were separated by filtration and washed with methanol (200
parts) to obtain a wet cake (31.5 parts). The resultant wet cake
was dried at 80.degree. C. to obtain copper
dibenzobis(2,3-pyrazino)porphyrazine di(sodium sulfonate) (mixture,
22.2 parts) as blue crystals. The blue crystals were analyzed. As a
result, the maximum absorption wavelength (.lamda..sub.max) thereof
was 610.5 nm (in an aqueous solution). From this result, the
resultant blue crystals were identified as Compound (17) having the
above structure.
(2) Synthesis of copper dibenzobis(2,3-pyrazino)-porphyrazine
di(sulfonyl chloride) [the following Compound (18): a mixture in
which two of outermost aromatic rings of a main component in the
mixture are pyrazine rings, and the remainder are benzene
rings]:
##STR00060##
Copper dibenzobis(2,3-pyrazino)porphyrazine di-(sodium sulfate)
(7.8 parts) obtained in the step (1) was gradually added to
chlorosulfonic acid (62.7 parts) under stirring while keeping the
temperature of the liquid at 60.degree. C. or less. Thereafter, a
reaction was conducted for 4 hours at 120.degree. C. The reaction
liquid was then cooled to 70.degree. C., and thionyl chloride (17.9
parts) was added dropwise over 30 minutes to conduct a reaction for
3 hours at 70.degree. C. The reaction liquid was cooled to
30.degree. C. or less and slowly poured into ice water (500 parts),
and crystals deposited were separated by filtration and washed with
cold water (200 parts) to obtain a wet cake (44.1 parts) of copper
dibenzobis(2,3-pyrazino)-porphyrazine di(sulfonyl chloride)
(mixture).
(3) Synthesis of the following Compound (19) [a mixture containing
Exemplified Compounds I-11 and I-12: a mixture in which two of
outermost aromatic rings of a main component in the mixture are
pyrazine rings, the remainder are benzene rings, b is 1.2, and c is
0.8]:
##STR00061##
The wet cake (44.1 parts) of copper
dibenzobis(2,3-pyrazino)porphyrazine di(sulfonyl chloride)
(Compound (18)) obtained in the step (2) was added into ice water
(200 parts) and suspended under stirring. A solution of Compound
(1) (purity: 59.3%, 20.5 parts) obtained upon the synthesis of
Compound 1-1 dissolved in aqueous ammonia (3.0 parts) and warm
water (100 parts) was then added to the suspension. The pH of the
reaction liquid was kept at 9.0 to 9.3 by adding 28% aqueous
ammonia thereto, and the temperature of the reaction liquid was
controlled to 17 to 20.degree. C. to conduct a reaction for 2
hours. Thereafter, the reaction liquid was heated to 60.degree. C.
The amount of the reaction liquid at this time was 450 parts.
Sodium chloride (90 parts, 20% to the amount of the reaction
liquid) was added to this reaction liquid, and 35% hydrochloric
acid was added to adjust the pH of the reaction liquid to 1.0,
thereby depositing crystals. The crystals deposited were separated
by filtration and washed with a 20% aqueous solution (100 parts) of
sodium chloride to obtain a wet cake (31.7 parts). After the
resultant wet cake was dissolved in water again, and the pH of the
resultant solution was adjusted to 9.0, the whole amount was
controlled to 300 parts, and the temperature of the solution was
raised to 60.degree. C. The amount of the solution at this time was
320 parts. Sodium chloride (64 parts, 20% to the amount of the
solution) was added to the solution, and 35% hydrochloric acid was
added to adjust the pH of the solution to 1.0, thereby depositing
crystals. The crystals deposited were separated by filtration and
washed with a 20% aqueous solution (100 parts) of sodium chloride
to obtain a wet cake (38.1 parts). After the resultant wet cake
(38.1 parts) was added into methanol (210 parts) and the resultant
mixture was stirred for 1 hour at 60.degree. C. to suspend the wet
cake, filtration, washing with methanol (200 parts) and drying were
conducted to obtain blue crystals (Compound (19), 8.8 parts). The
blue crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) was 614.5 nm (in an aqueous solution).
The resultant Compound (19) was subjected to ion exchange according
to a method known per se in the art to obtain Compound 1-6 of a
sodium salt type.
[Synthesis of Compound 1-7]
(1) Synthesis of a mixture of copper
tribenzo(2,3-pyrido)porphyrazine and copper
dibenzobis(2,3-pyrido)-porphyrazine [a mixture in which the ratio
of the pyridine ring to the benzene ring among A, B, C and D in the
general formula (A) is 1.5:2.5 on the average]
Sulfolane (250 parts), phthalimide (18.4 parts), quinolinic acid
(12.5 parts), urea (72.0 parts), copper(II) chloride dihydrate
(purity: 97.0%; 8.8 parts) and ammonium molybdate (1.0 part) were
added into a 4-necked flask, and the reaction liquid was heated to
200.degree. C. and held for 5 hours. After completion of the
reaction, the reaction liquid was cooled to 65.degree. C., methanol
(200 parts) was added, and crystals deposited were separated by
filtration. The resultant crystals were washed with methanol (150
parts) and then with warm water (200 parts) to obtain a wet cake
(72.2 parts). The resultant wet cake was added to 5% hydrochloric
acid (500 parts), and this liquid was heated to 60.degree. C. and
held for 1 hour. The resultant crystals were separated by
filtration and washed with water (200 parts). The resultant wet
cake was then added into 10% aqueous ammonia (500 parts), and the
temperature of the liquid was controlled to 60.degree. C. and held
for 1 hour. Thereafter, the resultant crystals were separated by
filtration and then washed with water (300 parts) and then with
methanol (100 parts) to obtain a wet cake (33.6 parts). The
resultant wet cake was dried at 80.degree. C. to obtain a mixture
(19.8 parts) of copper tribenzo(2,3-pyrido)porphyrazine and copper
dibenzobis-(2,3-pyrido)porphyrazine as blue crystals. The blue
crystals were analyzed. As a result, the maximum absorption
wavelength (.lamda..sub.max) thereof was 663.5 nm (in
pyridine).
(2) Synthesis of a mixture of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride) and copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride) [a mixture
containing Compound (3) and Compound (5): a mixture in which the
ratio of the pyridine ring to the benzene ring among A, B, C and D
in the general formula (B) is 1.5:2.5 on the average, and x is
2.5]:
The mixture (5.8 parts) of copper tribenzo(2,3-pyrido)porphyrazine
and copper dibenzobis-(2,3-pyrido)-porphyrazine obtained in the
step (1) was gradually added to chlorosulfonic acid (46.2 parts)
under stirring while keeping the temperature of the liquid at
60.degree. C. or less. Thereafter, a reaction was conducted for 4
hours at 140.degree. C. The reaction liquid was then cooled to
70.degree. C., and thionyl chloride (17.9 parts) was added dropwise
over 30 minutes to conduct a reaction for 3 hours at 70.degree. C.
The reaction liquid was cooled to 30.degree. C. or less and slowly
poured into ice water (500 parts), and crystals deposited were
separated by filtration and washed with cold water (200 parts). In
such a manner, a wet cake (59.3 parts) of a mixture of copper
tribenzo(2,3-pyrido)porphyrazine tri(sulfonyl chloride) and copper
dibenzobis(2,3-pyrido)porphyrazine di(sulfonyl chloride) was
obtained.
(3) Synthesis of a mixture of Compound (4) and Compound (16) [a
mixture containing Exemplified Compounds I-2, I-3 and I-4: a
mixture in which the ratio of the pyridine ring to the benzene ring
among A, B, C and D in the general formula (I) is 1.5:2.5 on the
average, E is ethylene, X is a 2,5-disulfoanilino group, Y is an
amino group, l is 0, m is 1.7, and n is 0.8]:
The wet cake (59.3 parts) of the mixture of copper
benzo(2,3-pyrido)porphyrazine sulfonyl chlorides obtained in the
step (2) was added into ice water (350 parts) and suspended under
stirring. A solution of Compound (1) (purity: 59.3%, 20.5 parts)
obtained upon the synthesis of Compound 1-1 dissolved in aqueous
ammonia (3.0 parts) and warm water (100 parts) was then added to
the suspension. The pH of the reaction liquid was kept at 9.0 to
9.3 by adding 28% aqueous ammonia thereto, and the temperature of
the reaction liquid was controlled to 17 to 20.degree. C. to
conduct a reaction for 4 hours. Thereafter, the reaction liquid was
heated to 60.degree. C. The amount of the reaction liquid at this
time was 560 parts. Sodium chloride (112 parts, 20% to the amount
of the reaction liquid) was added to this reaction liquid, and 35%
hydrochloric acid was added to adjust the pH of the reaction liquid
to 1.0, thereby depositing crystals. The crystals deposited were
separated by filtration and washed with a 20% aqueous solution (100
parts) of sodium chloride to obtain a wet cake (73.6 parts). After
the resultant wet cake was dissolved in water again, and the pH of
the resultant solution was adjusted to 9.0, the whole amount was
controlled to 360 parts, and the temperature of the solution was
raised to 60.degree. C. The amount of the solution at this time was
380 parts. Sodium chloride (76 parts, 20% to the amount of the
solution) was added to the solution, and 35% hydrochloric acid was
added to adjust the pH of the solution to 1.0, thereby depositing
crystals. The crystals deposited were separated by filtration and
washed with a 20% aqueous solution (100 parts) of sodium chloride
to obtain a wet cake (48.4 parts). After the resultant wet cake
(48.4 parts) was added into methanol (250 parts) and the resultant
mixture was stirred for 1 hour at 60.degree. C. to suspend the wet
cake, filtration, washing with methanol (200 parts) and drying were
conducted to obtain blue crystals (10.7 parts). The blue crystals
were analyzed. As a result, the maximum absorption wavelength
(.lamda..sub.max) was 606 nm (in an aqueous solution). The
resultant blue crystals were subjected to ion exchange according to
a method known per se in the art to obtain Compound 1-7 of a sodium
salt type.
[Compound 2]
The sodium salt of Exemplified Compound I-25 synthesized referring
to Japanese Patent Application Laid-Open No. 2006-45535 was used as
Compound 2.
Comparative Example 1
The following cyan dye synthesized referring to Japanese Patent No.
3851569 was used as Comparative Compound 1 that is a comparative
compound of the first coloring material.
##STR00062##
Compound 3 that is the second coloring material used in Examples
was synthesized in the following manner.
[Compound 3]
Compound 3 (potassium salt of Exemplified Compound II-5) was
synthesized according to the following synthesis flow and
procedure. Each flow is described in detail.
##STR00063##
(1) Synthesis of Compound b:
Sodium hydrogencarbonate (25.5 g) and ion-exchanged water (150 mL)
were mixed and heated to 40.degree. C., cyanuric chloride (product
of Tokyo Kasei; Compound a, 25.0 g) was added to this mixture by
successively adding five equally divided portions thereof at
intervals of 10 minutes, and the resultant mixture was stirred for
1 hour to prepare a solution. The resultant solution was added
dropwise to a mixed liquid (8.degree. C.) of hydrazine monohydrate
(52.8 mL) and ion-exchanged water (47 mL) in such a manner that the
internal temperature does not exceed 10.degree. C. Thereafter, the
internal temperature was raised to 50.degree. C., and the mixture
was stirred for 30 minutes. Crystals deposited were separated by
filtration to obtain Compound b (hydrazine derivative, melting
point: >300.degree. C., 23.4 g). The yield was 94.7%.
(2) Synthesis of Compound c:
Compound b (hydrazine derivative, 35.0 g) obtained above was
suspended in ethylene glycol (420 mL), the internal temperature was
raised to 50.degree. C., and the suspension was stirred.
Concentrated hydrochloric acid (59 mL) was added to this
suspension, pivaloylacetonitrile (product of Tokyo Kasei, 60.1 g)
was then added, and the resultant mixture was stirred for 10 hours
at 50.degree. C. Concentrated hydrochloric acid (95 mL) and
methanol (145 mL) were added thereto, and the mixture was
additionally stirred for 8 hours. After the mixture was cooled to
room temperature, crystals deposited were separated by filtration
to obtain Compound c (5-aminopyrazole derivative, melting point:
233 to 235.degree. C., 81.6 g). The yield was 94.2%.
(3) Synthesis of Compound e:
Compound d (product of Tokyo Kasei, 90.57 g) was suspended in water
(500 mL), concentrated hydrochloric acid (130 mL) was added to this
suspension, and the mixture was stirred until the internal
temperature after the addition reached 5.degree. C. or less. An
aqueous solution (70 mL) containing sodium nitrite (36.23 g) was
added dropwise in an internal temperature range of from 4 to
6.degree. C., and the resultant mixture was stirred for 30 minutes
at an internal temperature of 5.degree. C. or less. Sodium sulfite
(159 g) and water (636 mL) were then added while keeping the
internal temperature at 20.degree. C. or less, the internal
temperature was raised to 25.degree. C., concentrated hydrochloric
acid (250 mL) was added, and the resultant mixture was stirred for
1 hour at an internal temperature of 90.degree. C. After the
internal temperature was lowered to room temperature, filtration
was conducted, and the resultant residue was washed with water (200
mL) and air-dried to obtain Compound e (80.0 g).
(4) Synthesis of Compound f:
Compound e (23.3 g) obtained above was suspended in ethanol (209
mL), and triethylamine (28 mL) was added dropwise to this
suspension. Ethoxymethylene-malononitrile (product of ALDRICH, 12.2
g) was then added to this mixture in several divided portions.
After refluxing was conducted for 3 hours, the reaction mixture was
cooled to room temperature and filtered, and the product was washed
with isopropyl alcohol (400 mL) and then dried to obtain Compound f
(23.57 g).
(5) Synthesis of Compound 3:
Acetic acid (145.56 mL) was added to sulfuric acid (32.4 mL) at an
internal temperature of 4.degree. C. or less, and 40% by mass
nitrosylsulfuric acid (product of ALDRICH, 15.9 mL) was added
dropwise at an internal temperature of 7.degree. C. or less under
stirring. Compound f (32.4 g) obtained above was added to this
mixture in several divided portions, and the resultant mixture was
stirred for 60 minutes at an internal temperature of 10.degree. C.
Thereafter, a diazonium salt of Compound f was added dropwise into
a liquid suspension in which Compound c (18.8 g) to which urea
(1.83 g) had been added was suspended in methanol (470 mL) at an
internal temperature of 0.degree. C. or less, and the resultant
mixture was stirred for 30 minutes at an internal temperature of
0.degree. C. or less. Thereafter, the internal temperature of the
reaction liquid was raised to room temperature, the reaction liquid
is then filtered and washed with methanol and then with water to
obtain crude crystals. After the resultant crude crystals were
suspended in methanol (400 mL), and the suspension was stirred for
60 minutes under reflux, the suspension was cooled to room
temperature, filtered and washed with methanol, water and methanol
in that order, and then dried overnight at 75.degree. C. to obtain
free acid type crystals (34.4 g) of Compound 3. The resultant
crystals were dissolved in water to prepare a 10% by mass aqueous
solution (25.degree. C.; pH: about 8.3, adjusted with KOH), and
isopropanol was then added at an internal temperature of 50.degree.
C. to conduct crystallization, the reaction mixture was then
cooled, and the resultant crystals were separated by filtration,
washed with isopropanol and dried. In such a manner, Compound 3
(potassium salt of Exemplified Compound II-5, 35.0 g) was
obtained.
[Comparative Compound 2]
Comparative Compound 2 was used as a comparative compound of the
second coloring material. Comparative Compound 2 is a commercially
available yellow dye (Y104; product of ILFORD IMAGING) having the
following structure.
##STR00064##
Compound 4 that is the third coloring material used in Examples was
synthesized according to the following procedures (A) to (G).
Compound 4 was obtained as the sodium salt of Exemplified Compound
III-1. Compounds 5 and 6 that are the third coloring material used
in Examples were synthesized by methods described below. Compound
5w as synthesized as the sodium salt of Exemplified Compound IV-1
and Compound 6 was synthesized as the lithium salt of Exemplified
Compound V-2, respectively. Comparative Compounds 3 and 4 that are
magenta dyes used in Comparative Examples were synthesized by
methods described below.
[Compound 4]
(A) A compound (94.8 parts) of the following formula (I), sodium
carbonate (3.0 parts) and benzoyl ethyl acetate (144.0 parts) were
successively added to xylene (360 parts) under stirring, and the
temperature of the liquid was raised to 140 to 150.degree. C. to
conduct a reaction for 8 hours, during which ethanol and water,
which were formed by the reaction, were distilled out of the system
while being azeotropically distilled together with xylene, thereby
completing the reaction. The reaction liquid was cooled to
30.degree. C., methanol (240 parts) was added, and the resultant
mixture was stirred for 30 minutes. Thereafter, solids deposited
were separated by filtration. The resultant solids were washed with
methanol (360 parts) and the dried to obtain a compound (124.8
parts) of the following formula (2) as light yellow needlelike
crystals.
##STR00065##
##STR00066##
(B) The compound (88.8 parts) of the formula (2) obtained above,
metaaminoacetonitride (75.0 parts), copper acetate monohydrate
(24.0 parts) and sodium carbonate (12.8 parts) were successively
added into N,N-dimethylformamide (300.0 parts). The temperature of
the liquid was raised to 120 to 130.degree. C. to conduct a
reaction for 3 hours. The reaction liquid was cooled to about
50.degree. C., methanol (120 part) was added, and the resultant
mixture was stirred for 30 minutes. Thereafter, solids deposited
were separated by filtration. The resultant solids were washed with
methanol (500 parts) and then with warm water of 80.degree. C., and
then dried to obtain a compound (79.2 parts) of the following
formula (3) as bluish red crystals.
##STR00067##
(C) 28% Fumed sulfuric acid (170 parts) was added to 98% sulfuric
acid (130 parts) under stirring while cooling with water to prepare
12% fumed sulfuric acid (300 parts). After the compound (51.3
parts) of the formula (3) obtained above was added at a temperature
50.degree. C. or less while cooling with water, the temperature of
the liquid was raised to 85 to 90.degree. C. to conduct a reaction
for 4 hours. The reaction liquid was added into ice water (600
parts), during which rise of liquid temperature was prevented by
adding ice, thereby keeping the liquid temperature at 40.degree. C.
or less. Water was additionally added to increase the quantity of
the reaction liquid to 1,000 parts, and the insoluble matter was
then removed by filtration. Warm water was added to the resultant
mother liquor to 1,500 parts, sodium chloride (300 parts) was added
while keeping the liquid temperature at 60 to 65.degree. C., the
resultant mixture was stirred for 2 hours, and crystals deposited
were separated by filtration. The resultant crystals were washed
with a 20% aqueous solution (300 parts) of sodium chloride, and
water was fully removed to obtain a wet cake (100.3 parts)
containing a compound (59.2 parts) as red crystals.
##STR00068##
(D) The wet cake (67.7 parts) of the compound of the formula (4)
obtained above was added into water (60 parts). A 25% aqueous
solution (24 parts) of sodium hydroxide was added to this mixture,
and the mixture was stirred to prepare a solution while adjusting
the pH of the liquid to 3 to 4 by further adding a 25% aqueous
solution of sodium hydroxide. On the other hand, LIPAL OH (trade
name, anionic surfactant; product of Lion Corporation, 0.4 parts)
was added to ice water (60 parts), to which cyanuric chloride (8.9
parts) was added, and the mixture was stirred for 30 minutes to
obtain a suspension. The resultant suspension was added into the
solution containing the compound of the formula (4) obtained above.
A reaction was conducted for 4 hours at a temperature of 25 to
30.degree. C. while keeping the pH of the liquid at 2.7 to 3.0 with
a 10% aqueous solution of sodium hydroxide, thereby obtaining a
reaction mixture containing a compound of the following formula
(5).
##STR00069##
(E) Sodium p-phenolsulfonate dihydrate (9.5 parts) was added into
the reaction liquid containing the compound of the formula (5)
obtained above. The temperature of the liquid was then raised to 50
to 55.degree. C. while keeping the pH of the liquid at 6.5.+-.0.3
by adding a 25% aqueous solution of sodium hydroxide to this
liquid, and a reaction was conducted for 1 hour at the same
temperature, thereby obtaining a reaction mixture containing a
compound of the following formula (6).
##STR00070##
(F) Ethylenediamine (1.2 parts) was added into the reaction mixture
containing the compound of the formula (6) obtained above. The
temperature of the liquid was then raised to 78 to 82.degree. C.
while keeping the pH of the liquid at 7.8 to 8.2 by adding a 25%
aqueous solution of sodium hydroxide to this liquid, and a reaction
was conducted for 1 hour at the same temperature. After water was
then added to increase the quantity of the liquid to about 360
parts, filtration was conducted to remove the insoluble matter.
After water was added to the resultant mother liquor, and the
quantity of the liquid was increased to 400 parts, concentrated
hydrochloric acid was added while keeping the temperature of the
liquid at 55.+-.2.degree. C., thereby adjusting the pH of the
liquid to 3. Sodium chloride (40 parts) was added to this liquid
over 15 minutes, the resultant mixture was stirred, and
concentrated hydrochloric acid was additionally added to adjust the
pH of the liquid to 2. The resultant acidic aqueous solution was
stirred for 1 hour, crystals deposited were separated by
filtration, and the resultant crystals were washed with a 20%
aqueous solution (100 parts) of sodium chloride, thereby obtaining
a red wet cake.
(G) The wet cake obtained above was added into methanol (500
parts), the temperature of the liquid was raised to 60 to
65.degree. C., and the liquid was stirred for 1 hour. Crystals
deposited were separated by filtration, washed with methanol and
then dried, thereby obtaining Compound 4 of a free acid type. The
Compound 4 of the free acid type was subjected to ion exchange
according to a method known per se in the art to obtain Compound 4
(sodium salt of Exemplified Compound III-1).
[Compound 5]
The sodium salt of Exemplified Compound IV-1 synthesized referring
to the description of Example 4 in International Publication No.
2004/104108 Pamphlet was used as Compound 5.
[Compound 6]
The lithium salt of Exemplified Compound V-2 synthesized referring
to the description of Compound d-5 in Japanese Patent Application
Laid-Open No. 2006-143989 was used as Compound 6.
[Comparative Compound 3]
The following magenta dye synthesized referring to Japanese Patent
Application Laid-Open No. 2002-080765 was used as Comparative
Compound 3 that is a comparative compound of the third coloring
material.
##STR00071##
[Comparative Compound 4]
The following magenta dye synthesized referring to Japanese Patent
Application Laid-Open No. H8-073791 was used as Comparative
Compound 4 that is a comparative compound of the third coloring
material.
##STR00072##
Compound 7 and Compound 8 that are the fourth coloring material
used in Examples were synthesized by methods described below.
Compound 7 is the sodium salt of Exemplified Compound VI-1, and
Compound 8 is the sodium salt of Exemplified Compound VII-5.
Comparative Compound 5 that is a black dye used in Comparative
Example was synthesized by a method described below.
[Compound 7]
The sodium salt of Exemplified Compound VI-1 synthesized referring
to the description of Example 1 in International Publication No.
2006/001274 Pamphlet was used as Compound 7.
[Compound 8]
The lithium salt of Exemplified Compound VII-5 synthesized
referring to Japanese Patent Application Laid-Open No. 2005-139427
was used as Compound 8.
[Comparative Compound 5]
The following black dye synthesized referring to U.S. Pat. No.
6,302,949 was used as Comparative Compound 5 that is a comparative
compound of the fourth coloring material.
##STR00073##
<Evaluation of Combination of Cyan Dye and Yellow Dye>
The combination of coloring materials was variously changed to
prepare inks of Examples 1 to 15 and Comparative Examples 1 to 5 in
the following manner. Compounds 1-1 to 1-7 and Compound 2
synthesized above were used as the first coloring material for
Examples, and Comparative Compound 1 synthesized above and C.I.
Direct Blue 199 were used for comparison thereof. Compound 3
synthesized above, and C.I. Direct Yellow 132 and C.I. Direct
Yellow 86 were used as the second coloring material for Examples
and Comparative Examples, respectively. First, the components shown
in the following Table 5 were mixed and sufficiently stirred. The
resultant respective mixtures were then filtered under pressure
through a filter having a pore size of 0.2 .mu.m to prepare inks of
Examples and Comparative Examples. The cyan dyes of each Compound
1-1 to 1-7 and Compound 2 correspond to the first coloring
material, and the yellow dye of Compound 3 corresponds to the
second coloring material.
TABLE-US-00008 TABLE 5 Compositions of Inks (Unit: % by mass)
Example 1 2 3 4 5 6 7 Cyan dye Compound 1-1 1.20 1.79 1.80 2.20
Compound 1-2 2.20 Compound 1-3 2.20 Compound 1-4 Compound 1-5
Compound 1-6 Compound 1-7 Compound 2 1.20 Comparative Compound 1
C.I. Direct Blue 199 Yellow dye Compound 3 2.40 2.40 1.81 1.80 1.40
1.40 1.40 C.I. Direct Yellow 132 C.I. Direct Yellow 86 Ethylene
glycol 9.00 9.00 9.00 9.00 9.00 9.00 9.00 Diethylene glycol 9.00
9.00 9.00 9.00 9.00 9.00 9.00 Acetylenol E100 (*1) 1.00 1.00 1.00
1.00 1.00 1.00 1.00 Ion-exchanged water 77.40 77.40 77.40 77.40
77.40 77.40 77.40 First coloring 0.50 0.50 0.99 1.00 1.57 1.57 1.57
material/second coloring material (*2) Example 8 9 10 11 12 13 14
15 Cyan dye Compound 1-1 3.00 3.20 3.21 3.30 Compound 1-2 Compound
1-3 Compound 1-4 2.20 Compound 1-5 2.20 Compound 1-6 2.20 Compound
1-7 2.20 Compound 2 Comparative Compound 1 C.I. Direct Blue 199
Yellow dye Compound 3 1.40 1.40 1.40 1.40 0.60 0.40 0.39 0.30 C.I.
Direct Yellow 132 C.I. Direct Yellow 86 Ethylene glycol 9.00 9.00
9.00 9.00 9.00 9.00 9.00 9.00 Diethylene 9.00 9.00 9.00 9.00 9.00
9.00 9.00 9.00 glycol Acetylenol E100 (*1) 1.00 1.00 1.00 1.00 1.00
1.00 1.00 1.00 Ion-exchanged 77.40 77.40 77.40 77.40 77.40 77.40
77.40 77.40 water First coloring 1.57 1.57 1.57 1.57 5.00 8.00 8.23
11.00 material/second coloring material (*2) Comparative Example 1
2 3 4 5 Cyan dye Compound 1-1 1.20 1.20 Compound 1-2 Compound 1-3
Compound 1-4 Compound 1-5 Compound 1-6 Compound 1-7 Compound 2
Comparative 1.20 1.20 Compound 1 C.I. Direct 1.20 Blue 199 Yellow
dye Compound 3 2.40 2.40 C.I. Direct 2.40 Yellow 132 C.I. Direct
2.40 2.40 Yellow 86 Ethylene glycol 9.00 9.00 9.00 9.00 9.00
Diethylene glycol 9.00 9.00 9.00 9.00 9.00 Acetylenol E100 (*1)
1.00 1.00 1.00 1.00 1.00 Ion-exchanged water 77.40 77.40 77.40
77.40 77.40 First coloring -- -- 0.00 0.00 -- material/second
coloring material (*2) (*1) Acetylene glycol ethylene oxide adduct
(surfactant; Product of Kawaken Fine Chemicals Co., Ltd.) (*2)
Content of first coloring material/content of second coloring
material.
[Evaluation]
Each of the inks obtained above was charged into an ink jet
recording apparatus (trade name: PIXUS iP8600); manufactured by
Canon Inc.) utilizing thermal energy. Recording conditions were set
to 23.degree. C. in temperature, 55% in relative humidity, 2,400
dpi.times.1,200 dpi in recording density and 2.5 .mu.L in ejection
quantity. Images were respectively formed on a recording medium
(Professional Photo Paper PR-101; product of Canon Inc.) with the
recording duty changed at intervals of 10% from 0% to 100%.
With respect to an image portion in which the recording duty was
50% in the recorded article obtained above, lightness (L) and color
tone (a and b) in the L*a*b* color space prescribed by CIE
(International Commission on Illumination) were measured (referred
to as "Lab value before ozone fastness test"). This recorded
article was exposed to ozone for 2 cycles (1 cycle: exposure for 16
hours) under conditions of 2.5 ppm in ozone gas concentration, 50%
in relative humidity and 23.degree. C. in vessel temperature by
means of an ozone exposure tester (trade name: OMS-H; manufactured
by SUGA TEST INSTRUMENTS CO., LTD.). Thereafter, with respect to
the image portion in which the recording duty was 50% in the
recorded article, lightness (L) and color tone (a and b) were
measured in the same manner as described above (referred to as "Lab
value after ozone fastness test"). Incidentally, the lightness (L)
and color tone (a and b) were measured by means of a
spectrophotometer (trade name: Spectrolino; manufactured by Gretag
Macbeth) under conditions of a light source: D50 and an angle of
field: 2.degree.. A color difference (.DELTA.E) was calculated out
from the Lab values before the ozone fastness test and the Lab
values after the ozone fastness test according to the following
equation (A) to make evaluation as to ozone fastness. The
evaluation standard of the ozone fastness is as follows. The
evaluation results are shown in Table 6. Incidentally, the ratio
between the contents of the first coloring material and the second
coloring material is shown collectively in Table 6.
In the following evaluation standard, AA, A and B are levels of
causing no problem as ozone fastness, A is an excellent level, AA
is a particularly excellent level, and C is a level unallowable as
ozone fastness. .DELTA.E= {square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
} Formula (A) L.sub.1, a.sub.1, b.sub.1: Lab value before ozone
fastness test L.sub.2, a.sub.2, b.sub.2: Lab value after ozone
fastness test AA: .DELTA.E is less than 5; A: .DELTA.E is from 5 or
more to less than 7; B: .DELTA.E is from 7 or more to less than 10;
C: .DELTA.E is 10 or more.
TABLE-US-00009 TABLE 6 Evaluation results First coloring material/
Ozone fastness second coloring material Example 1 B 0.50 Example 2
A 0.50 Example 3 A 0.99 Example 4 AA 1.00 Example 5 AA 1.57 Example
6 AA 1.57 Example 7 AA 1.57 Example 8 AA 1.57 Example 9 AA 1.57
Example 10 AA 1.57 Example 11 AA 1.57 Example 12 AA 5.00 Example 13
AA 8.00 Example 14 A 8.23 Example 15 A 11.00 Comparative C --
Example 1 Comparative C -- Example 2 Comparative C 0.00 Example 3
Comparative C 0.00 Example 4 Comparative C -- Example 5
[d Value]
With respect to the respective inks of Examples 1 and 2, and
Comparative Example 4 obtained above, and Compound 1-1, Compound 2
and Comparative Compound 1, scattering angle profiles were measured
by a small angle X-ray scattering method. Incidentally, the
measurement as to each ink was conducted by preparing a model ink
with the water-soluble organic solvent and surfactant in each ink
composition replaced by water, and hence the measurement was
conducted as to an aqueous dye solution containing a combination of
a cyan dye and a yellow dye in an actual ink composition. The
measurement as to each dye was conducted by preparing an aqueous
dye solution so as to give a dye concentration of 3.5% by mass.
Measuring conditions of the scattering angle profile are as
follows: Apparatus: Nano Viewer (manufactured by Rigaku Co.) X-ray
source: Cu-K.alpha. Output: 45 kV-60 mA Effective focal point: 0.3
mm .phi.+Confocal Max-Flux Mirror First slit: 0.5 mm, second slit:
0.4 mm, third slit: 0.8 mm Irradiation time: 240 minutes Beam
stopper: 3.0 mm .phi. Measuring method: transmission method
Detector: Blue Imaging Plate.
From the resultant scattering angle profile, a d value (nm) was
calculated out from a 2.theta. value of a scattering angle peak top
using an X-ray diffraction processing software JADE (product of
Material Data Inc.). Incidentally, the d value is an index of the
aggregation property or dispersion property of a coloring
material.
.lamda..times..times..times..times..theta..times..times.
##EQU00001## wherein .lamda. is a wavelength of an X-ray, d is an
interparticle distance, and .theta. is a scattering angle.
The d value thus obtained is as follows:
TABLE-US-00010 Ink of Example 1: 5.89 nm Ink of Example 2: 5.68 nm
Ink of Comparative Example 4: 6.09 nm Compound 1-1: 6.77 nm
Compound 2: 6.98 nm Comparative Compound 1 6.84 nm.
<Evaluation of Gray Ink>
(Preparation of inks of Examples 16 to 46 and Comparative Examples
6 to 12)
Compounds 1-1 to 1-17, Compounds 2 to 8 and Comparative Compounds 1
to 5 obtained by the above-described respective syntheses, and C.I.
Direct Yellow 86 were used to prepare respective inks of Examples
and Comparative Examples in the following manner. First, the
components shown in Table 7 were mixed and sufficiently stirred.
The resultant respective mixtures were then filtered under pressure
through a filter having a pore size of 0.2 .mu.m to prepare the
respective inks.
In the following Table 7-1 to 7-6, (*1) to (*4) indicates "note",
and the details thereof are as follows. Incidentally, "Bal" in
Table 7-1 to 7-6 means that adjustment was conducted with
ion-exchanged water in such a manner that the whole composition of
each ink amounts to 100%. Specifically, the remainder obtained by
subtracting the values of respective ink components from 100
becomes the amount of water. (*1) Acetylene glycol ethylene oxide
adduct (surfactant; Product of Kawaken Fine Chemicals Co., Ltd.)
(*2) Content of first coloring material/content of second coloring
material (*3) (Content of first coloring material+content of second
coloring material)/content of third coloring material (*4) (Content
of first coloring material+content of second coloring
material+content of third coloring material added as
needed)/content of fourth coloring material.
Incidentally, when the respective coloring materials defined in the
present invention were used in Comparative Examples, the contents
of the corresponding coloring materials were calculated and
indicated. The cyan dyes of each Compound 1-1 to 1-7 and compound 2
correspond to the first coloring material, the yellow dye of
compound 3 corresponds to the second coloring material, the magenta
dye of the Compound 4 to 6 correspond to the third coloring
material, and the black dye of the Compound 7 and 8 correspond to
the fourth coloring material.
TABLE-US-00011 TABLE 7-1 Compositions of Inks (Unit: % by mass)
Example 16 17 18 19 20 21 22 23 Cyan Compound 1-1 1.40 1.40 1.40
1.40 1.40 1.40 1.40 Compound 1-2 Compound 1-3 Compound 1-4 Compound
1-5 Compound 1-6 Compound 1-7 Compound 2 1.40 Comparative Compound
1 Yellow Compound 3 0.85 0.85 0.85 0.85 0.85 0.85 0.85 0.85
Comparative Compound 2 C.I. Direct Yellow 86 Magenta Compound 4
1.00 2.25 0.75 2.50 0.73 Compound 5 1.00 1.00 Compound 6 1.00
Comparative Compound 3 Comparative Compound 4 Black Compound 7
Compound 8 Comparative Compound 5 Ethylene glycol 9.00 9.00 9.00
9.00 9.00 9.00 9.00 9.00 Diethylene 9.00 9.00 9.00 9.00 9.00 9.00
9.00 9.00 glycol Acetylenol 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
E100 (*1) Ion-exchanged Bal Bal Bal Bal Bal Bal Bal Bal water
First/second 1.65 1.65 1.65 1.65 1.65 1.65 1.65 1.65 (*2) (First +
2.25 2.25 1.00 3.00 0.90 3.08 2.25 2.25 second)/third (*3) (First +
-- -- -- -- -- -- -- -- second + third)/fourth (*4)
TABLE-US-00012 TABLE 7-2 Compositions of Inks (Unit: % by mass)
Example 24 25 26 27 28 29 30 Cyan Compound 1-1 1.40 1.40 1.40 1.40
1.40 1.40 Compound 1-2 Compound 1-3 Compound 1-4 Compound 1-5
Compound 1-6 Compound 1-7 Compound 2 1.40 Comparative Compound 1
Yellow Compound 3 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Comparative
Compound 2 C.I. Direct Yellow 86 Magenta Compound 4 Compound 5
Compound 6 1.00 1.00 1.00 1.00 1.00 1.00 Comparative Compound 3
Comparative 1.00 Compound 4 Black Compound 7 0.10 0.65 0.073 0.66
0.072 0.10 Compound 8 Comparative Compound 5 Ethylene glycol 9.00
9.00 9.00 9.00 9.00 9.00 9.00 Diethylene 9.00 9.00 9.00 9.00 9.00
9.00 9.00 glycol Acetylenol E100 1.00 1.00 1.00 1.00 1.00 1.00 1.00
(*1) Ion-exchanged Bal Bal Bal Bal Bal Bal Bal water First/second
1.65 1.65 1.65 1.65 1.65 1.65 1.65 (*2) (First + second)/ -- 2.25
2.25 2.25 2.25 2.25 2.25 third (*3) (First + second + -- 32.50 5.00
44.52 4.92 45.14 32.50 third)/fourth (*4)
TABLE-US-00013 TABLE 7-3 Compositions of Inks (Unit: % by mass)
Example 31 32 33 34 35 36 Cyan Compound 1-1 1.40 1.40 1.40 1.40
1.40 Compound 1-2 Compound 1-3 Compound 1-4 Compound 1-5 Compound
1-6 Compound 1-7 Compound 2 1.40 Comparative Compound 1 Yellow
Compound 3 0.85 0.85 0.85 0.85 0.85 0.85 Comparative Compound 2
C.I. Direct Yellow 86 Magenta Compound 4 Compound 5 Compound 6 1.00
1.00 1.00 1.00 1.00 1.00 Comparative Compound 3 Comparative
Compound 4 Black Compound 7 Compound 8 0.10 0.65 0.073 0.66 0.072
0.10 Comparative Compound 5 Ethylene glycol 9.00 9.00 9.00 9.00
9.00 9.00 Diethylene 9.00 9.00 9.00 9.00 9.00 9.00 glycol
Acetylenol E100 1.00 1.00 1.00 1.00 1.00 1.00 (*1) Ion-exchanged
Bal Bal Bal Bal Bal Bal water First/second 1.65 1.65 1.65 1.65 1.65
1.65 (*2) (First + second)/ 2.25 2.25 2.25 2.25 2.25 2.25 third
(*3) (First + second + 32.50 5.00 44.52 4.92 45.14 32.50
third)/fourth (*4)
TABLE-US-00014 TABLE 7-4 Compositions of Inks (Unit: % by mass)
Example 37 38 39 40 41 42 43 Cyan Compound 1-1 Compound 1-2 1.40
Compound 1-3 1.40 Compound 1-4 1.40 Compound 1-5 1.40 Compound 1-6
1.40 Compound 1-7 1.40 1.40 Compound 2 Comparative Compound 1
Yellow Compound 3 0.85 0.85 0.85 0.85 0.85 0.85 0.85 Comparative
Compound 2 C.I. Direct Yellow 86 Magenta Compound 4 Compound 5
Compound 6 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Comparative Compound
3 Comparative Compound 4 Black Compound 7 0.10 Compound 8 0.10 0.10
0.10 0.10 0.10 0.10 0.10 Comparative Compound 5 Ethylene glycol
9.00 9.00 9.00 9.00 9.00 9.00 9.00 Diethylene 9.00 9.00 9.00 9.00
9.00 9.00 9.00 glycol Acetylenol E100 1.00 1.00 1.00 1.00 1.00 1.00
1.00 (*1) Ion exchanged Bal Bal Bal Bal Bal Bal Bal water
First/second 1.65 1.65 1.65 1.65 1.65 1.65 1.65 (*2) (First +
second)/ 2.25 2.25 2.25 2.25 2.25 2.25 2.25 third (*3) (First +
second + 32.50 32.50 32.50 32.50 32.50 32.50 16.25 third)/fourth
(*4)
TABLE-US-00015 TABLE 7-5 Compositions of Inks (Unit: % by mass)
Example 44 45 46 Cyan Compound 1-1 1.40 1.40 1.40 Compound 1-2
Compound 1-3 Compound 1-4 Compound 1-5 Compound 1-6 Compound 1-7
Compound 2 Comparative Compound 1 Yellow Compound 3 0.85 0.85 0.85
Comparative Compound 2 C.I. Direct Yellow 86 Magenta Compound 4
Compound 5 Compound 6 1.00 Comparative 1.00 1.00 Compound 3
Comparative Compound 4 Black Compound 7 0.10 Compound 8 0.10
Comparative 0.10 Compound 5 Ethylene glycol 9.00 9.00 9.00
Diethylene glycol 9.00 9.00 9.00 Acetylenol E100 (*1) 1.00 1.00
1.00 Ion-exchanged water Bal Bal Bal First/second (*2) 1.65 1.65
1.65 (First + second)/third (*3) -- -- 2.25 (First + second +
third)/ 22.5 22.5 -- fourth (*4)
TABLE-US-00016 TABLE 7-6 Compositions of Inks (Unit: % by mass)
Comparative Example 6 7 8 9 10 11 12 Cyan Compound 1-1 1.40 1.40
1.40 Compound 1-2 Compound 1-3 Compound 1-4 Compound 1-5 Compound
1-6 Compound 1-7 Compound 2 Comparative 1.40 1.40 1.40 Compound 1
Yellow Compound 3 0.85 0.85 0.85 Comparative 1.80 Compound 2 C.I.
Direct 0.85 0.85 0.85 Yellow 86 Magenta Compound 4 Compound 5
Compound 6 1.00 1.00 1.00 1.00 1.00 1.00 Comparative 0.40 Compound
3 Comparative Compound 4 Black Compound 7 0.10 0.10 Compound 8 0.10
0.10 Comparative 4.50 Compound 5 Ethylene glycol 9.00 9.00 9.00
9.00 9.00 9.00 9.00 Diethylene glycol 9.00 9.00 9.00 9.00 9.00 9.00
9.00 Acetylenol E100 (*1) 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Ion-exchanged water Bal Bal Bal Bal Bal Bal Bal First/second (*2)
0.00 -- 0.00 0.00 -- -- -- (First + second)/third (*3) 0.85 1.40
0.85 0.85 1.40 1.40 -- (First + second + third)/ -- -- 18.50 18.50
24.00 24.00 -- fourth (*4)
(Evaluation)
Each of the inks obtained above was charged into an ink jet
recording apparatus (trade name: PIXUS iP8600); manufactured by
Canon Inc.) utilizing thermal energy. Recording conditions were set
to 23.degree. C. in temperature, 55% in relative humidity, 2,400
dpi.times.1,200 dpi in recording density and 2.5 pL in ejection
quantity. Images were respectively formed on a recording medium
(Professional Photo Paper PR-101; product of Canon Inc.) with the
recording duty changed at intervals of 10% from 0% to 100%.
[Ozone Fastness]
With respect to an image portion in which the recording duty was
50% in the recorded article obtained above, lightness (L) and color
tone (a and b) in the L*a*b* color space prescribed by CIE
(International Commission on Illumination) were measured (referred
to as "Lab value before ozone fastness test"). This recorded
article was exposed to ozone for 2 cycles (1 cycle: exposure for 16
hours) under conditions of 2.5 ppm in ozone gas concentration, 50%
in relative humidity and 23.degree. C. in vessel temperature by
means of an ozone exposure tester (trade name: OMS-H; manufactured
by SUGA TEST INSTRUMENTS CO., LTD.). Thereafter, with respect to
the image portion in which the recording duty was 50% in the
recorded article, lightness (L) and color tone (a and b) were
measured in the same manner as described above (referred to as "Lab
value after ozone fastness test"). Incidentally, the lightness (L)
and color tone (a and b) were measured by means of a
spectrophotometer (trade name: Spectrolino; manufactured by Gretag
Macbeth) under conditions of a light source: D50 and an angle of
field: 2.degree.. A color difference (.DELTA.E) was calculated out
from the Lab values before the ozone fastness test and the Lab
values after the ozone fastness test according to the following
equation (A) to make evaluation as to ozone fastness.
The evaluation standard of the ozone fastness is as follows. The
evaluation results are shown in Table 8. Incidentally, content
ratios among the respective combinations of the first to fourth
coloring materials are shown collectively in Table 8. In the
following evaluation standard, A and B are levels of causing no
problem as ozone fastness, A is an excellent level and C is a level
unallowable as ozone fastness. .DELTA.E= {square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
} Formula (A) L.sub.1, a.sub.1, b.sub.1: Lab value before ozone
fastness test L.sub.2, a.sub.2, b.sub.2: Lab value after ozone
fastness test A: .DELTA.E is less than 8.5; B: .DELTA.E is from 8.5
or more to less than 10; C: .DELTA.E is 10 or more.
[Light Fastness]
With respect to an image portion in which the recording duty was
50% in the recorded article obtained above, lightness (L) and color
tone (a and b) in the L*a*b* color space prescribed by CIE
(International Commission on Illumination) were measured (referred
to as "Lab value before light fastness test"). This recorded
article was exposed to light by means of a low-temperature xenon
tester (trade name: SL-75; manufactured by SUGA TEST INSTRUMENTS
CO., LTD.) for 220 hours under conditions of 50 klx in irradiation
intensity, 50% in relative humidity and 23.degree. C. in vessel
temperature. Thereafter, with respect to the image portion in which
the recording duty was 50% in the recorded article, lightness (L)
and color tone (a and b) were measured in the same manner as
described above (referred to as "Lab value after light fastness
test"). Incidentally, the lightness (L) and color tone (a and b)
were measured by means of a spectrophotometer (trade name:
Spectrolino; manufactured by Gretag Macbeth) under conditions of a
light source: D50 and an angle of field: 2.degree.. A color
difference (.DELTA.E) was calculated out from the Lab values before
the light fastness test and the Lab values after the light fastness
test according to the following equation (B) to make evaluation as
to light fastness.
The evaluation standard of the light fastness is as follows. The
evaluation results are shown in Table 8. In the following
evaluation standard, AA, A and B are levels of causing no problem
as light fastness, A is an excellent level, AA is a particularly
excellent level, and C is a level unallowable as light fastness.
.DELTA.E= {square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
} Formula (B) L.sub.1, a.sub.1, b.sub.1: Lab value before light
fastness test L.sub.2, a.sub.2, b.sub.2: Lab value after light
fastness test AA: .DELTA.E is less than 5; A: .DELTA.E is from 5 or
more to less than 7; B: .DELTA.E is from 7 or more to less than 10;
C: .DELTA.E is 10 or more.
[Color Tone]
With respect to an image portion in which the recording duty was
100% in the recorded article obtained above, a* and b* in the
L*a*b* color space prescribed by CIE (International Commission on
Illumination) were measured to make evaluation as to color tone.
Incidentally, a* and b* were measured by means of a
spectrophotometer (trade name: Spectrolino; manufactured by Gretag
Macbeth) under conditions of a light source: D50 and an angle of
field: 2.degree..
The evaluation standard of the color tone is as follows. The
evaluation results are shown in Table 8. In the following
evaluation standard, A and B are levels of causing no problem as
color tone, A is an excellent level, and C is a level unallowable
as color tone. A: Satisfying -0.5.ltoreq.a*.ltoreq.5 and
-6.5.ltoreq.b*.ltoreq.0; B: Satisfying -5.ltoreq.a*.ltoreq.10 and
-10.ltoreq.b*.ltoreq.1, but not satisfying -0.5.ltoreq.a*.ltoreq.5
and -6.5.ltoreq.b*.ltoreq.0; C: Not satisfying -5<a*<10 and
-10<b*<1.
[Metamerism]
With respect to an image portion in which the recording duty was
100% in the recorded article obtained above, L*, a* and b* in the
L*a*b* color space prescribed by CIE (International Commission on
Illumination) were measured. Incidentally, the measurement of L*,
a* and b* was conducted by measuring a reflection absorption
spectrum by means of a spectrophotometer (trade name: Spectrolino;
manufactured by Gretag Macbeth) under conditions of light sources:
D50, D65, A, C and F1 to F12, and an angle of field: 2.degree.. At
this time, the L*, a* and b* values when the light source was D50
were referred to as "L*, a* and b* values in the light source of
D50", and the L*, a* and b* values when the light sources were D65,
A, C and F1 to F12 (15 types in total) were referred to as "L*, a*
and b* values in the respective light sources". Based on the L*, a*
and b* values when the light source was D50, a deviation of the L*,
a* and b* values in each of the light sources of the 15 types was
calculated out as a color difference (.DELTA.E) according to the
following equation (C). Metamerism was evaluated from an average
value (average value of .DELTA.E) of the color differences obtained
by the respective light sources of the 15 types.
The evaluation standard of the metamerism is as follows. The
evaluation results are shown in Table 8. In the following
evaluation standard, A and B are levels causing no problem as
metamerism, A is an excellent level, and C is a level unallowable
as metamerism. .DELTA.E= {square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
}{square root over
((L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2+(b.sub.1-b.sub.2).sup.2)-
} Formula (C) L.sub.1, a.sub.1, b.sub.1: Lab value in the light
source of D50 L.sub.2, a.sub.2, b.sub.2: Lab value in the
respective light sources A: 0.0.ltoreq.average value of
.DELTA.E.ltoreq.4.0; B: 4.0<average value of
.DELTA.E.ltoreq.5.0; C: 5.0<average value of .DELTA.E.
TABLE-US-00017 TABLE 8-1 Evaluation results of Examples Content
ratio among 1.sup.st to 4.sup.th coloring materials (1.sup.st +
Color Ozone Light (1.sup.st + 2.sup.nd)/ 2.sup.nd + tone fastness
fastness Metamerism 1.sup.st /2.sup.nd 3.sup.rd 3.sup.rd)/4.sup.th
Example 16 A A A B 1.65 2.25 -- 17 B A A B 1.65 2.25 -- 18 B A A B
1.65 1.00 -- 19 B A A B 1.65 3.00 -- 20 B A B B 1.65 0.90 -- 21 B A
B B 1.65 3.08 -- 22 B A A B 1.65 2.25 -- 23 A B A B 1.65 2.25 -- 24
B B B B 1.65 -- -- 25 A A AA B 1.65 2.25 32.50 26 A A AA B 1.65
2.25 5.00 27 A A AA B 1.65 2.25 44.52 28 B A AA B 1.65 2.25 4.92 29
B A AA B 1.65 2.25 45.14 30 A B AA B 1.65 2.25 32.50 31 A A AA A
1.65 2.25 32.50 32 A A AA A 1.65 2.25 5.00 33 A A AA A 1.65 2.25
44.52 34 A A A A 1.65 2.25 4.92 35 A A A A 1.65 2.25 45.14 36 A B
AA A 1.65 2.25 32.50 37 A A AA A 1.65 2.25 32.50 38 A A AA A 1.65
2.25 32.50 39 A A AA A 1.65 2.25 32.50 40 A A AA A 1.65 2.25 32.50
41 A A AA A 1.65 2.25 32.50 42 A A AA A 1.65 2.25 32.50 43 A A AA A
1.65 2.25 16.25 44 B B B B 1.65 -- 22.50 45 B B B A 1.65 -- 22.50
46 B B B B 1.65 2.25 --
.DELTA.E values of Examples 24 and 44 to 46 were lower than that of
the Examples that had the evaluation results of the ozone fastness
of B. .DELTA.E value of Example 24 was lower than that of the
Examples that had the evaluation results of the light fastness of
B.
TABLE-US-00018 TABLE 8-2 Evaluation results of Comparative Examples
Color Ozone Light tone fastness fastness Metamerism Note Comp. A B
B C Containing none of Ex. 6 1.sup.st to 4.sup.th coloring
materials Comp. A C C A Containing none of Ex. 7 2.sup.nd to
4.sup.th coloring materials Comp. A B B C Containing no 1.sup.st
Ex. 8 coloring material Comp. A B B B Containing no 1.sup.st Ex. 9
coloring material Comp. B C C C Containing no 2.sup.nd Ex. 10
coloring material Comp. B C C B Containing no 2.sup.nd Ex. 11
coloring material Comp. C C B B Containing none of Ex. 12 1.sup.st
to 4.sup.th coloring materials
Incidentally, specific examples of other respective substituents
and structures embraced in the above-described compounds than the
above-described embodiments are not mentioned herein, but the
effects achieved by the above embodiments could be achieved
likewise.
While the present invention has been described with reference to
exemplary embodiments, it is to be understood that the invention is
not limited to the disclosed exemplary embodiments. The scope of
the following claims is to be accorded the broadest interpretation
so as to encompass all such modifications and equivalent structures
and functions.
This application claims the benefit of Japanese Patent Applications
No. 2007-210095, filed Aug. 10, 2007, and No. 2008-175247, filed
Jul. 4, 2008, which are hereby incorporated by reference herein in
their entirety.
* * * * *